Handbook of Polymers in Electronics

Bansi D. Malhotra

Handbook of Polymers in Electronics

Bansi D. Malhotra

Rapra Technology Limited
Shawbury, Shrewsbury, Shropshire, SY4 4NR, United Kingdom Telephone: +44 (0)1939 250383 Fax: +44 (0)1939 251118 http://www.rapra.net

First Published in 2002 by

Rapra Technology Limited
Shawbury, Shrewsbury, Shropshire, SY4 4NR, UK

©2002, Rapra Technology Limited

All rights reserved. Except as permitted under current legislation no part of this publication may be photocopied, reproduced or distributed in any form or by any means or stored in a database or retrieval system, without the prior permission from the copyright holder. A catalogue record for this book is available from the British Library.

ISBN: 1-85957-286-3

Typeset by Rapra Technology Limited Printed and bound by Polestar Scientifica, Exeter, UK



Charge Transport in Conjugated Polymers ...................................................... 3 1.1 1.2 1.3 Introduction ........................................................................................... 3 The Electronic Ground State .................................................................. 4 Charge Transport Carriers ..................................................................... 6 1.3.1 1.3.2 1.4 1.5 Soliton ....................................................................................... 7 Polaron and Bipolaron ............................................................... 9

Transport Properties of Polymers ......................................................... 12 Factors Influencing the Transport Properties of Polymers .................... 14 1.5.1 1.5.2 1.5.3 Disorder ................................................................................... 14 Doping ..................................................................................... 15 Interchain Coupling ................................................................. 17

1.6 1.7

Models of Charge Transport in Conducting Polymers ......................... 18 Conclusions ......................................................................................... 27

Acknowledgements ....................................................................................... 28 References ..................................................................................................... 28 2 Electrical Properties of Doped Conjugated Polymers .................................... 37 2.1 2.2 Introduction ......................................................................................... 37 Metallic State ....................................................................................... 39 2.2.1 2.2.2 2.2.3 2.2.4 2.3 Conductivity ............................................................................ 40 Magnetoconductance ............................................................... 50 Thermoelectric Power .............................................................. 55 Magnetic Susceptibility and Specific Heat................................ 56

Critical and Insulating States ............................................................... 58

Polymers in Electronics


Summary .............................................................................................. 63

References ..................................................................................................... 65 3 Non Linear Optical Properties of Polymers for Electronics ........................... 69 3.1 3.2 3.3 Introduction ......................................................................................... 69 NLO Polymer Issues for Device Applications ...................................... 70 Properties of Third-Order NLO Polymers ........................................... 71 3.3.1 3.3.2 3.3.3 3.3.4 3.3.5 3.3.6 Background of Third-Order NLO Polymer Research .............. 71 Poly(arylenevinylene), PAV ...................................................... 72 n-BCMU-PDA ......................................................................... 75 PT ............................................................................................ 76 Processible π-Conjugated Polymers .......................................... 76 Third-Order NLO Polymer Waveguides .................................. 82

3.4. Properties of Second-Order NLO Polymers ......................................... 84 3.4.1 3.4.2 3.4.3 3.4.4 3.5 3.6 Azo-Dye-Functionalised, Poled Polymers for Second-Order Non Linear Optics ................................................................... 84 EO Polymers ............................................................................ 87 Serially-Grafted Polymer Waveguides ...................................... 88 Refractive Index Grating Fabrication into Azo-Dye- ................... Functionalised Polymer Waveguides ........................................ 90

Future Targets of NLO Polymers for Optical Device Applications ...... 93 Conclusions ......................................................................................... 94

Acknowledgements ....................................................................................... 94 References ..................................................................................................... 94 4 Luminescence Studies of Polymers ................................................................ 99 4.1 4.2 Introduction ......................................................................................... 99 Basic Photophysical Deactivation Processes ....................................... 100 4.2.1 4.2.2

Luminescence ......................................................................... 101 Bimolecular Photophysical Processes ..................................... 103


4.2.3 4.3

Quenching Processes .............................................................. 104

Methods for Fluorescence Studies ...................................................... 105 4.3.1 4.3.2 Time-Correlated Single-Photon Counting Studies .................. 105 Quantum Yields ..................................................................... 105


Fluorescence of Polymers, Excimer Fluorescence ............................... 106 4.4.1 4.4.2 Fluorescence of Polymers in Solution ..................................... 110 Fluorescence of Polymers in Gel State .................................... 122


Conclusions ....................................................................................... 136

Acknowledgements ..................................................................................... 136 References ................................................................................................... 136 5 Polymers for Light Emitting Diodes ............................................................ 141 5.1 5.2 Introduction ....................................................................................... 141 The Physics of Electroluminescent Devices ........................................ 142 5.2.1 5.2.2 5.2.3 5.3 The Physics of Conjugated Polymers ..................................... 142 The Physics of the Device....................................................... 144 LED Characterisation ............................................................ 147

Polymeric Structures for LED ............................................................ 148 5.3.1 5.3.2 Polyphenylenes ...................................................................... 148 Polythiophenes ....................................................................... 164


Recent Developments ......................................................................... 168 5.4.1 5.4.2 5.4.3 Polarised Electroluminescence ............................................... 168 Lifetime and Degradation in LEDs ........................................ 170 Microcavities ......................................................................... 170


Concluding Remarks ......................................................................... 171

References ................................................................................................... 172 6 Photopolymers and Photoresists for Electronics .......................................... 185 6.1 Introduction ....................................................................................... 185


Polymers in Electronics


Microlithography Process .................................................................. 187 6.2.1 6.2.2 6.2.3 6.2.4 6.2.5 6.2.6 6.2.7 Resist Coating ........................................................................ 188 Exposure ................................................................................ 188 Development .......................................................................... 189 Post Baking ............................................................................ 190 Etching .................................................................................. 190 Resist Removal (Stripping) .................................................... 190 Doping ................................................................................... 190


Resist Requirements ........................................................................... 190 6.3.1 6.3.2 6.3.3 6.3.4 Solubility ............................................................................... 191 Adhesion ................................................................................ 191 Etching Resistance ................................................................. 191 Sensitivity and Contrast ......................................................... 191


Resist Materials ................................................................................. 193 6.4.1 6.4.2 6.4.3 6.4.4 6.4.5 Conventional Photoresists ..................................................... 193 Deep-UV Photoresists ............................................................ 197 Electron-Beam Resists ............................................................ 202 X-Ray Resists ........................................................................ 206 Special Resists ........................................................................ 208


Conclusions ....................................................................................... 212

References ................................................................................................... 212 7 Polymer Batteries for Electronics ................................................................. 217 7.1 7.2 Introduction ....................................................................................... 217 Ionically Conducting Polymers .......................................................... 218 7.2.1 7.2.2 7.3 Lithium Polymer Electrolytes and Lithium Batteries .............. 218 Proton Polymer Electrolytes ................................................... 239

Electronically Conducting Polymers .................................................. 242 7.3.1 Lithium-Doped Conducting Polymer and LithiumPolymer Batteries ................................................................... 243



Acknowledgements ..................................................................................... 245 References ................................................................................................... 245 8 Polymer Microactuators .............................................................................. 255 8.1 8.2 8.3 8.4 8.5 8.6 8.7 8.8 8.9 Introduction ....................................................................................... 255 Sample Preparation and Measurements of Electrolytic Deformation . 257 Electrochemistry and Expansion Behaviour in Polyaniline Film ......... 259 Dependencies of the Expansion Ratio on the Degree of Oxidation and Dopant Ions ................................................................................ 260 pH Dependence of Electrolytic Expansion ......................................... 262 Time Response of the Electrolytic Expansion..................................... 265 Anisotropy of Electrolytic Expansion in Polyaniline Films ................. 266 Contraction Under Strain in Stretched Polyaniline Films ................... 267 Electrolytic Expansion in Other Conducting Polymers ...................... 267

8.10 Applications of Electrolytic Expansion .............................................. 268 8.11 Conclusions ....................................................................................... 269 References ................................................................................................... 269 9 Membranes for Electronics ......................................................................... 271 9.1 9.2 Introduction ....................................................................................... 271 Plasma Polymerisation ....................................................................... 276 9.2.1 9.2.2 9.2.3 9.3 History .................................................................................. 277 General Characteristics .......................................................... 277 Synthesis of Plasma Polymers ................................................ 278

Characterisation of Plasma Polymers ................................................. 282 9.3.1 9.3.2 IR Spectroscopy ..................................................................... 283 XPS ........................................................................................ 283


Applications of Plasma Polymers ....................................................... 283


..4...........................4..................................5 Importance of Conducting Polymers to Biosensors ................... 286 Resist Films ..4 Effect of Storage Time ...................4..................4.....2 Effect of pH ............................... 285 Conductive Films ...............................................3............3 9.......................1.............................. 309 10.....4.........Polymers in Electronics 9.............. 298 10..............................5 9... 313 vi ..............................4..................4................................ 309 10..........4................ 309 10................................ 284 Semiconductive Films .....................................4.................................7 9....3....... 297 10.........................4.......1 Methods of Immobilisation....................................................................................2 Advantages of Immobilisation ...................... 299 10..................................................................................1.......................................4 Biological Component .....................1............................................ 287 Acknowledgements ...... 302 10.................... 297 10....................................................................................5 Response Measurements .................1 Introduction ........................ 305 10.....3 Effect of Temperature .......3 Immobilisation of Biomolecules/Enzymes ..... 305 10.............6 9.............1..............................8 Packaging ............................................................................................ 304 10............................ 301 10....3 Transducers .............. 311 10.....2 Conduction Mechanism in Conducting Polymers .2 9......1 Biosensors ........................ 290 References .............................. 304 10........................... 287 Biosensors ...................... 286 Ultrathin Polymer Films .... 284 Insulator ....................................................... 312 10... 310 10.............. 286 Chemical Sensors ...2................................................................................................4 Characterisation of Enzyme Electrodes ......4......2 Construction of Biosensors ....................................................2 Preparation of Electrodes ..............4................ 301 10....1 Determination of Enzyme Activity ... 291 10 Conducting Polymer-Based Biosensors .........................2..................4..............1.. 305 10.....................................................................1 Synthesis of Conducting Polymers .........4 9.....................1 9........................................

........3 Lactate Biosensor ..........................................................................................................................2 Material Preparation Methods .......9 Conclusions ....... 353 11..1 Glucose Biosensor ....2 Electrochemical Biosensors ...........................5 DNA Biosensor ....... 367 12........................................... 315 10.............................1 Introduction .......................................................4 Summary . 361 12 Polymers for Electronics .... 327 11 Nanoparticle-Dispersed Semiconducting Polymers for Electronics ..................... 320 10............................................................. 314 10...................6.............................................................................3...6...................................7 Immunosensor ...........................................................8 Biosensors for Environmental Monitoring ................... 321 10...... 361 References . 313 10....4 Cholesterol Biosensor ...........................................................................5 Types of Biosensors ..................... 368 12........... 327 References ............................ 323 10............... 324 10..................................3.............. 344 11............. 326 10...........................2 Urea Biosensor ...6................1 Introduction ................ 346 11...............................1 TiO2-Conjugated Polymer Composites ................... 326 10............................................................................... 326 Acknowledgements .......................... 341 11....................................... 341 11.................6 Biosensors for Healthcare ....................................................................................... 357 11.................................................5..........................3............. 348 11.............................................................................................3 Conduction in Polymers .........Contents 10...................................................... 375 vii ....................................................6.............................................................. 318 10......6................3 Gold-Polythiophene Blends ................................................................... 360 Acknowledgements .1 Optical Biosensors ... 367 12..... 318 10................................2 Polymer Electroluminescence .........5...3 Photophysics of Charge Separation Nanoparticle-Polymer Systems .......................2 Nanoparticle Semiconductors-Polymer Systems ...................................................................................................................................................

................................. 379 12.6 Conclusions ................... 393 13.......2 Self-Assembly Monolayers ................................................................ 406 Field-Effect Transistor ............................................................................................................................................................ 399 13...................................................... 418 Electroluminescent Displays .............5................ 423 13....................................................................................................................... 399 13...............................4 Characterisation of Conducting Polymers .7 13.............................................. 397 13...............5 Polymer Deposition Technologies .......................8 Diodes ............................6 13................................................. 425 Abbreviations and Acronyms........................................................................................................5..................................... 379 12...........3 Preparation of Ultrathin Conducting Polymer Films ............................ 415 Nanowires .......................................... 419 Microactuators .........................................................5....................................................................................................................................................................................................................................................................5.. 388 Acknowledgements ..................... 425 References ..............5...............5 13.................... 409 Biosensors .........................................................2 Synthesis of Conducting Polymers ................ 406 13................3..6 Summary ...............................................5.............................3 13.... 411 Electronic Tongue .5 Molecular Devices Based on Conducting Polymers .....1 Introduction .......... 424 Acknowledgements ............................................................. 404 13................................5...............4 13.........4 Molecular Electronics .................................................1 Langmuir-Blodgett Films ...... 453 viii ......................................................................................Polymers in Electronics 12...................3....................... 449 Index ...................................................2 13............. 441 Contributors ...... 393 13............... 388 13 Conducting Polymers in Molecular Electronics ......... 388 References .......... 414 Electronic Nose ...5.............................1 13............. 404 13...............

However. Alberto Bolognesi and cowriters (Chapter 5) reveal that polymers offer a 1 . conjugated polymers have been projected to have innumerable applications in electronics and are thus presently at the centre-stage of research and development. It is anticipated that polymers may perhaps offer viable solutions to the problems presently being confronted by the modern electronics industry.Preface There is a global effort towards the applications of polymers in electronics. light-weight batteries. i. optical and photo-physical properties will go a long way in bridging a long-felt industrial need and motivate the dedicated and younger researchers to venture into new experiments. photonics. Among the various polymeric materials.e. It is indicated that an improved understanding of the mechanism of charge transport in these materials is likely to unravel new hidden phenomena having implications in polymer electronics. characterisation and potential applications of polymers coupled with the fundamentals of the electrical. It was thus thought that a Handbook dedicated entirely to the preparation. Reghu Menon (Chapter 2) discusses the role of easily polarisable delocalised p-electrons in determining the electrical properties of conducting polymers. Vibha Saxena and cowriters (Chapter 1) discuss the phenomenon of charge transport in electrically conducting polymers. micro-actuators. chemical un-saturation of the carbon atoms in the polymer chain. considered to be a direct consequence of conjugation. The demand for new polymeric materials that can replace the widely used semi-conductor silicon in microelectronics has recently intensified.. biosensors and molecular electronics. ‘Handbook of Polymers in Electronics’ has been designed to discuss novel ways polymers can be used in the rapidly growing electronics industry. Barbara Wandelt (Chapter 4) in her extensive coverage of the luminescence properties of polymers reveals how fluorescence probes can provide an insight into the nature of intermolecular interactions in these systems. Conducting polymers have been found to have applications in a wide range of emerging areas such as light-emitting diodes. manufacturing and commercial establishments located worldwide. it may be noted that development of polymers for electronics is still an open field wherein polymers are used not only as insulators but can also be tailored for the desired electronic properties for specific applications. Recent developments in microelectronics have prompted enhanced interest towards the search for new molecular materials that can be utilised for increased density of packaging. This has essentially been due to the continuing drive towards higher circuit density of the micro-electronic components and the muchneeded very high speed processing of the data being continuously generated in various research. Toshikuni Kaino (Chapter 3) focuses on the transmission and processing of digital information using conjugated non-linear optical devices based on polymers.

F. Jean-Claude Dubois (Chapter 6) discusses the technological developments of photopolymers and photo-resists presently being used in microelectronics industry.S. Mashelkar. Joshi. Tim Richardson (Chapter 12) deals with the various options available to a device engineer associated with the technological development of polymer based electronic devices.Handbook of Polymers in Electronics unique possibility of working with cheaper technology giving flexible films that can be used to emit light. New Delhi for the many discussions and suggestions during the operation of the project. The Handbook would not have been possible without the invaluable advice received on many occasions from a number of eminent scientists including Professor S. Raychaudhri. New Delhi for many discussions held during the implementation of the project. Saini. it would have been difficult to complete the project without the emotional support I received from Shashi (wife). Bruno Scrosati (Chapter 7) has provided an interesting insight into the potential of polymeric electrodes for lightweight batteries for applications in electronics. Chapter 13 contains a comprehensive review on molecular electronic applications of conducting polymers. K. Mr Steve Barnfield is thanked for the typesetting and the excellent cover design of the Handbook. Professor E. Dr. Dr A. Bansi D. Keeping this in view. in their outstanding appraisal (Chapter 8).S. Ms Claire Griffiths.Narayan (Chapter 11) reveals a synergistic approach towards the nanoparticle dispersed particles semi-conducting polymers for application in miniaturised electronic devices. Gopal.K. Isao Karube and cowriters (Chapter 9) have given an excellent review of the preparation. Aditi (daughter) and Rajat (son). Dr Krishan Lal and Dr Howard H. I am thankful to all my colleagues especially Dr K. Dr W. Keiichi Kaneto and cowriters. Weetall.K. FRS. Bawa and Dr Subhas Chandra of NPL.A. Slomkowskii. I am thankful to all the members of my research group (Biomolecular Electronics & Conducting Polymers) of the National Physical Laboratory (NPL). Turner.P. ‘Polymers in Electronics’ is the result of the invaluable contributions of many celebrated researchers who have been active in their respective fields for many decades.S.R. characterisation of the plasma-polymerised membranes for application in electronics. Finally. I would also like to extend my thanks to Geoffrey Jones of Information Index who so skilfully produced the index. S. Conducting polymers have been predicted to play decisive role towards the fabrication of third generation biosensors. Dr R. Hayes. Professor A.K. Asha Chaubey and cowriters (Chapter 10) have shown that redox polymers can be advantageously used to combine both the role of protein immobilisation matrices and the physical transducer resulting in improved response characteristics and miniaturisation.Malhotra 2 . Dr Arshad Makhdum and Dr Sarah Ward of the editorial staff at Rapra have worked extremely hard to check that everything in the Handbook is correct and that the project is completed in time. have shown that the changes in molecular conformations arising due to the localisation of p-electrons and electronic repulsion between the polycations influence the operation of a conducting polymer micro-actuator. Professor S. Special thanks are due to Ms Frances Powers of Rapra for her timely suggestion that this project should be undertaken. I am grateful to all of them for their active participation in this important project.

Table 1.6 3 .1 Introduction Since the early 1950s. an inorganic conjugated polymer. Since then.0 2. the idea of using polymers for their electrical conducting properties actually emerged in 1977 with the findings of Shirakawa and co-workers [2]. polythiazyl. In 1975. (SN)x. high chemical inertness. poly(pphenylene) (PPP) and polycarbazole (PCz) [3-6] have been synthesised and studied. Saxena and B. these polymers (hereafter called conducting or conjugated polymers) have been extensively investigated for an understanding of their physical and chemical properties.29 K [1]. Some important conducting polymers and their energy gaps are shown in Table 1. polythiophene (PT). Malhotra 1. which possesses metallic conductivity and becomes a superconductor at 0.1 Important conducting polymers Polymer Trans-polyacetylene Cis-polyacetylene Polypyrrole Polythiophene Poly(p-phenylene) Poly(p-phenylenevinylene) Polyaniline Optical absorption edge (eV) 1.0 3.0 2. an active interest in synthesising other organic polymers possessing this property has been initiated. Since the beginning of the last decade. electrical insulation and ease of processing.1.4 1. flexibility. other polymers having a π-electron conjugated structure. (CH)x.1 Charge Transport in Conjugated Polymers V.D. exhibits conductivity of 103 S cm-1. corrosion resistance.5 2. polymers have been used extensively as passive components in electronic devices because of their light weight. such as polyaniline (PANI). was discovered. However. that the iodine-doped transpolyacetylene. As a result. polypyrrole (PPy). polyfuran (PFu).4 2.

the contributions from disorder and doping. such as polarons and bipolarons found in non degenerate groundstate systems. recent developments in reducing the extent of disorder have explained many phenomena regarding charge transport in doped conducting polymers. Therefore. The bands form by the splitting of the atomic levels when the atoms approach one another and obtain their equilibrium positions in the crystal. It is understood that a wide variety of phenomena are involved in charge transport in this group of materials. In a semiconductor. are produced due to the chain relaxation or deformation that results from adding/removing an electron from the polymeric chain. interchain interactions. make it difficult to estimate the contribution from individual parameters quantitatively. Each of these particles possesses its own characteristic transport properties. This excitation and other excitations. pressure. etc. A major source of this phenomenon originates from the quasi-one-dimensional (q-1D) nature of the materials.Handbook of Polymers in Electronics The charge transfer process is one of the most intriguing properties of conducting polymers because the electrical conductivities of this class of polymers vary over many orders of magnitude due to chemical or electrochemical doping. etc. Moreover.. a study of charge transport in conducting polymers is presented. The charge transfer properties as a function of temperature. this gap separates the band which is completely filled (valence band) from the lowest energy band which is completely empty at absolute zero (conduction band) and accounts for the conduction processes in 4 . such as electron-phonon interaction. In this chapter. The bands are separated by forbidden energy ranges called the energy gap. However. Under the influence of an applied electric field these non linear defects become mobile. This leads to a band structure responsible for the important electronic properties in polymers and thereby results in the existence of a non linear excitation called a soliton. which may be visualised as originating from the electronic levels of the atom. for various polymeric samples have also been reported in the literature. A polyconjugated chain can be considered as a q-1D metal. etc. It is a well-established fact that such a half-filled system gives rise to Peierls instability by opening up an insulating gap at the Fermi level. having one charge carrier per carbon atom. quantum lattice fluctuations. an overview of the past few years. resulting in an increased electrical conductivity. The collective contributions from various parameters. the theoretical modelling of transport properties in conducting polymers is still a challenging problem due to the extreme complexity of the system. magnetic fields. 1.. A clear understanding of the intrinsic excitations in doped and undoped conjugated polymers is still lacking [7-8]. make it rather difficult to envisage a microscopic mechanism for charge transport in doped conducting polymers.2 The Electronic Ground State It is well known that the accessible energy levels of an electron in a crystal are grouped into bands. electron-electron interaction. A considerable amount of work has been carried out by several researchers focusing on this fundamental problem..

generates an n-fold super-structure and reduces the Brillouin zone to –π/na<k<π/na. when electron-electron interactions dominate. these systems could be treated using Peierls theory. the conduction band is partially filled. with n being the number of atoms in the new unit cell. In contrast. implying that a finite density of states exists at the Fermi level. A periodic distortion of the chains.Charge Transport in Conjugated Polymers this class of materials. if only states below the new gap are Figure 1. commensurate with the original structure. Therefore. The Peierls model explains why a chain of unsaturated carbon atoms with one conduction electron per atom does not exhibit metallic properties. the basic cell in reciprocal space is the Brillouin zone in the interval –π/a<k<π/a (k is the wave vector). With one electron per atom. The formation of the band gap is explained taking into account either electron-phonon interactions or electronelectron interactions among π-electrons. If all the atoms are spaced at equal distance. If electron-phonon interaction dominates in real π-conjugated polymers. The effect of the distortion is to open a gap at the boundaries k = ±π/na of the new Brilliouin zone (Figure 1. In metals. where E is energy and EF is the Fermi energy 5 . a. Conjugated polymers differ from crystalline semiconductors and metals in several aspects and are often treated theoretically as a one-dimensional system. the Hubbard model could be used to explain the physical properties of polymers.1 One-dimensional electronic system with a half-filled band.1). band structure (a) before and (b) after Peierls distortion. the band would be halffilled and hence the chain would exhibit metallic behaviour.

implying that the semiconducting state is more stable than the metallic state. However. Considerable theoretical and experimental work has been carried out in this area [25-27]. This model provides an excellent intuitive framework and analytic benchmark for understanding the role of electron-electron interactions in a conducting polymer. pinning-depinning processes. the phase of the periodic lattice distortion can move through the lattice carrying a charge density wave. The Peierls-Hubbard model incorporates both the coulomb interaction among π-electrons and their coupling to lattice degrees of freedom [15]. in a three-dimensional array of one-dimensional chains. This model yields a gap in the absence of a Peierls distortion. For an exactly half-filled band this model gives insulating behaviour. In the simple Hubbard model. However. the Pariser-Parr-Pople model [22]. Some other important models are the Su-Schrieffer-Heeger model [20. If it is incommensurate. 1. the conductivity behaviour is observed. do play the role of charge carriers [23. but electron-phonon interaction is assumed to be negligible [14]. In such a case. 6 . The increased Frohlich conductivity in the Peierls state is rather sensitive to various extrinsic features such as disorder.Handbook of Polymers in Electronics occupied with electrons. Frohlich showed that the Peierls state is semiconducting only if the periodic lattice distortion is commensurate with the lattice [10]. electron correlation is taken into account. These models have been applied to simple polymers and found to agree with the experimental findings [16-19]. 24]. none of these models was found to satisfactorily explain all the physical properties of conducting polymers. The Peierls model completely neglects the coulomb repulsion for an electron that is transferred to a state already occupied. and the Mott-Hubbard model. The Peierls model clearly indicates that a one-dimensional chain of unsaturated carbon atoms leads invariably to a semiconducting state [9]. polarons and bipolarons. However. a reduction of the energy will occur and the distorted state will be more favourable.3 Charge Transport Carriers The nature of the charge carriers in conducting polymers is not very well understood. which have been used extensively to explain the features of these materials. the Peierls state is conducting. However. chain interaction. It is believed that intrinsic excitations. However. etc. such as solitons. A considerable amount of work has been reported in this area [11-13]. for the case deviating from the half-filled band condition. the quantum lattice fluctuations and the interchain coupling tend to reduce the Peierls gap. The properties of these excitations are discussed in detail in the following sections. to obtain a realistic description of these systems one needs to consider a model incorporating both electron-phonon and electron-electron interactions. The size of the single-particle gap (δ) is proportional to the amplitude of the lattice distortion (u). 21].

it is reported that solitons are delocalised over about 12 (CH) units [26]. The non bonding orbital corresponds to a soliton level at the middle of the forbidden gap. The addition or removal of one electron to the neutral state corresponds to a negative or positive soliton with zero spin (Figure 1. Therefore.Charge Transport in Conjugated Polymers 1. In a degenerate ground state.3. In the case of PAc. these cations are not bound to each other by any lattice distortion and can freely separate along the chain. the system has isoenergetic regions. solitons are isolated. Neutral.1 Soliton The probability of finding this excitation for conduction holds true for conjugated polymers with degenerate ground state structures such as trans-polyacetylene (PAc) (Figure 1. called a soliton. has a 1/2 spin with zero charge.3. Figure 1. one or two electrons. It may contain zero. because of the two-fold degeneracy of PAc. This excitation. non interacting charged defects that form domain walls separating two phases of opposite orientation with identical energies.2a). which can move along the chain without a distortion [25].4).2 Ground state energy (E) as a function of the configuration co-ordinate (Δ) for a system with a (a) degenerate and (b) non degenerate state 7 . For a neutral chain. negative and positive solitons in a trans-PAc chain are shown in Figure 1. which is a non bonding orbital occupied by a single electron. However. the soliton can be thought of as a 2pz unhybridised orbital of a sp2 hybridised carbon atom. Further oxidation of the polymer creates a dication.

nuclear magnetic resonance (NMR) spectroscopy and electron nuclear double resonance (ENDOR) measurements [13]. the reader is referred to a review article by Heeger and co-workers [13]. this excitation has also been studied in another degenerate ground state conjugate polymer. The onedimensional spin diffusion and associated spin dynamics are verified from electron magnetic resonance spectroscopy. more theoretical and experimental work is 8 . However.3 Formation of solitons in trans-polyacetylene: (a) neutral. (b) negative and (c) positive solitons Several experiments have been carried out to confirm the physical properties of solitons in trans-polyacetylene [27].Handbook of Polymers in Electronics (a) (b) (c) Figure 1. poly(1. The density of neutral solitons has been estimated by Motsovoy and co-workers [29]. Lately.4 Energy levels and localised level occupations of the (a) neutral. For more details on the physical properties of solitons. (b) positive and (c) negative soliton So (a) S(b) S+ (c) Figure 1.6-heptadiene) [28].

Like a free carrier. a polaron has a spin of 1/2 and a charge of ±e. Polaron formation creates new localised electronic states in the band gap (Figure 1. coulomb interaction. disorder. a single bond alternation defect in such a chain cannot behave as a charged soliton. Therefore. In the case of PPy. The lower energy states are occupied by a single unpaired electron. A polaron may be a radical cation (oxidation) or a radical anion (reduction). However.5 Formation of a polaron and a bipolaron in polypyrrole 9 . The radical cation is then coupled by a local bond rearrangement and a quinoid-like bond sequence is formed.. Figure 1. etc. because of the higher lattice energy of quinoid compared to benzenoid. The removal of an electron from a polymeric system creates a free radical and a positive charge.6). the lattice distortion is believed to extend over about four pyrrole rings. these distortions are limited.5 eV from the band edges [31]. Theoretical studies indicate that the polaron states of PPy are symmetrically located about 0. the energies of the two chains on either side of the defect are different (Figure 1.Charge Transport in Conjugated Polymers required in order to understand the influence of chain interaction.3. 1.2b). A charge injected on a chain is accompanied by a distortion in the chain and forms a polaron [30].2 Polaron and Bipolaron In the case of a non degenerate ground state. This combination of charged site coupled with a free radical via a local lattice distortion is called a polaron (Figure 1. on the physical properties of this excitation.5).

which are coupled through lattice distortion. a polaron radical is removed and two new positive charges result. resulting in metal-like conductivity. When a polymeric chain having a polaron is subjected to further oxidation. 33]. explicit 10 . In the latter case. it has been found that the conductivity of the system is spinless. about 0. two polarons are formed. which overlap to form continuous bipolaron bands. Later. It has been reported through quantum chemical calculations that bipolaron energies are lower than those of polarons by 0. but bipolaron bands tend to merge with the conduction band (CB) and valence band (VB). The experimental evidence of formation of polarons and bipolarons has been given by Bredas and co-workers by examination of the optical spectra of many doped conjugated polymers [32]. Therefore.4 eV [13].6 Energy levels and localised states for the (a) positive and (b) negative polarons In many cases. which suggests that charge carriers other than polarons would be appropriate in these cases [32.75 eV away from the band edges in case of PPy (Figure 1.Handbook of Polymers in Electronics Q=+e S = 1/2 (a) Q=-e S = 1/2 (b) Figure 1. the polymer band gap also increases. indicating that bipolaron formation is thermodynamically more favourable. However. During doping. Continuous doping of the polymer creates additional localised bipolaron states.7). Bipolaron states are located symmetrically within the band gap. it was proposed that polaron interaction would produce a new charge carrier with no spin and 2e charge corresponding to a positive bipolaron (Figure 1. In the former case.5). an electron is removed from either the polaron or the rest of the chain. The spectral and spin signatures of polaron pairs in πconjugated polymers have been reported by Lane and co-workers using photoinduced absorption and optically detected magnetic resonance (ODMR) [34]. the formation of a bipolaron causes a further decrease in ionisation compared to two polarons.

Conversely. Mizes and co-workers reported a study on the stability of polaron in trans-polyacetylene and poly(phenylene vinylene) [43]. In contrast.Charge Transport in Conjugated Polymers Q=2e S=0 (a) Q=-2e S=0 (b) Figure 1. The effect of conjugation is apparently 11 . the moving polaron structure is destroyed faster than the structure of moving bipolarons. The effect of an electric field on polarons and bipolarons in a single polymer chain has been investigated by Magela [41]. The stability of a bipolaron as a function of the strength of the long-range coulomb interaction with and without impurities has been studied in detail [42]. the existence of chain endings and other conjugation breaks are found to stabilise the polaron. Nevertheless. later. Being bound to a dopant. Emin and Nagai suggested that defect and disorder would tend to localise the polaron. A number of experimental and theoretical studies have dealt with the physical properties of polarons and bipolarons [36-40]. as the electric field intensity gets stronger. the bipolaron becomes stable in a wide range of coulomb interactions.7 Energy levels and occupied localised states for the (a) positive and (b) negative bipolaron evidence for bipolaron formation in conducting polymers has been provided by Ramsey and co-workers using ultraviolet photoelectron spectroscopy and electron-energy-loss spectroscopy [35]. However. It is found that dynamic effects do not reverse the stability relation between polarons and bipolarons. thus making the electron into a conduction band electron of the kind usually found in conventional semiconductors [44]. They pointed out that many defects and the short conjugation length in these materials would tend to stabilise the polaron [43]. Three-dimensional band structure calculations of these polymers indicate the destabilisation of polaron. Vogl and Campbell concluded (from local density functional calculations for polyacetylene) that the effect of interchain interaction is sufficient to destabilise a polaron. It is found that in a free state a bipolaron is stable only when the coulomb interaction is small (weak coupling limit) and it becomes unstable for strong coulomb interactions.

(i) when W(T) is greater than 0 at low temperature. Therefore. (iii)when W(T) is greater than 0 at low temperatures. the M-I transition in conducting polymers is determined by the extent of disorder. the current emphasis is on the metallic properties of these systems. Recent reports on the improved quality of the polymeric samples have substantially reduced the dominant role of the disorder.4 K)/ρ/(300 K). was first observed in the case of polyacetylene [47]. ρr~ρ/(1. We herein give a brief account of the metallic conductivity observed in these polymers. 1. A detailed study of polarons and bipolarons is given by Conwell and Mizes [46]. The reports of these studies have implications in the emerging field of molecular electronics (Chapter 13). etc. the data analysis was not focused on the precise identification of the metallic.. the system is near the insulating side of the M-I transition.1) 12 . defined as: W(T) = -T[dlnρ(T)/dT] = d(lnσ)/d(lnT) where σ is the conductivity. the system is on the critical regime of the M-I transition (i. in pinning and stabilising these excitations are not precisely known.. Being amorphous materials. critical and insulating regimes.Handbook of Polymers in Electronics sufficient to prevent such localisation [45]. (1. However. where the M-I transition is feasible). a great amount of work has been devoted to elucidating the conduction mechanism involved. Since then. In early publications. dopants. This hindered the clear understanding of the charge transport phenomenon in conducting polymers. the roles of disorder. as observed in the metal-insulator (M-I) transition. the resistivity ratio. The charge transport in these materials has been explained by dividing these materials into three regimes according to their reduced activation energy. interchain interaction.4 Transport Properties of Polymers The strong variation of the electrical conductivity of conjugated polymers upon doping. Another important parameter characterising the M-I transition is ρr. T is the temperature and ρ is the resistivity. the system is near the metallic side of the M-I transition. The transport properties of doped conducting polymers are given in Chapter 2 of this book.e. (ii) when W(T) is independent of temperature for a wide range of temperatures.

Here the second term in the equation arises from the electron-electron interaction and third term is the correction to σ(0) due to localisation effects. 13 . and m is a constant. 52-56]. The maximum room temperature conductivity parallel to the chain axis obtained by Naarman and subsequently by others is approximately 105 S cm-1. the spin dynamics being the same for both kind of polymers. The maximum value of intrinsic conductivity and stretchability of iodine-doped transpolyacetylene is very much dependent on the film thickness. These features show the presence of a continuous density of states with a well-defined Fermi energy. The extensive studies conducted on disordered metals in the past few years have shown that the absence of a significant positive TCR does not necessarily imply the system being non metallic. linear temperature dependence of the thermoelectric power down to 10 K. it is not an essential criterion for metallic behaviour. The conductivity in the disordered metals at low temperature is given by [50.2) where B is a constant depending on the localisation effects. 51]: σ(T) = σ(0) + mT1/2 + BT ρ/2 (1. σ(0) is the conductivity at absolute temperature. such as copper [48]. and large metallic reflectance in the infrared are other features observed in metallic polymers [49]. Another alternative method to determine the metallic state of polymers is the reduced activation energy as defined above. Although a positive temperature coefficient of resistance (TCR) is desirable for a good metal. In the clean limit: ρ = 3 for electron-phonon scattering ρ = 2 for inelastic electron-electron scattering ρ = 3/2 In the dirty limit: Among the various metallic conducting polymers studied so far. The value of ρ is determined by the temperature dependence of the scattering rate of the dominant dephasing mechanism. linear term in the specific heat at low temperatures. being roughly one-fifth of that of copper [57-60]. the thinner the film. Apart from this. temperature independent Pauli susceptibility down to 10 K. oriented transpolyacetylene has been studied the most [48. The main difference between polyacetylene synthesised by Shirakawa and Naarman is the higher density and degree of chain orientation in the latter case.Charge Transport in Conjugated Polymers Metallic polymers are defined as polymers having a finite conductivity at temperatures approaching absolute zero and a room temperature conductivity in the range of that of conventional metals. the higher the conductivity in both stretched and unstretched films [61].

Besides this. consistent with the observed coherence length. 1.5 Factors Influencing the Transport Properties of Polymers It may be remarked that the actual charge transport process in a conducting polymer is dependent on several parameters such as disorder (e. etc. For an intermediate temperature range (4-40 K). 1. leading to weak disorder. inelastic electronphonon scattering is found to be the dominant scattering mechanism. Disorder effects are known to produce tails in the bands of regular systems and this usually reduces the energy gap between valence and conduction bands [68].e. the process of preparation modifies the morphology and may lead to partial crystallinity. The different sources of disorder in a polymer include inhomogeneous doping that arises due to the nature of the catalyst used and also the processing routes.66]. The sign of temperature dependence indicates that the conductivity is limited by material imperfections such as tunneling/hopping regions and disordered metal regions. clusters. i. Heavily doped and highly disordered polyacetylene is almost metallic (the Peierls distortion is suppressed) resulting in a mean free path of about 100 Å. etc. presence of vacancies. On the other hand. Thummes and coworkers have emphasised that the conductivity of doped polyacetylene at low temperatures follows a T1/2 law indicating that electron-electron interactions play a dominant role at very low temperatures [65 .Handbook of Polymers in Electronics The transport properties of heavily doped Naarman polyacetylene have been reviewed by Paasch [62]..g. interchain coupling. The temperature dependence of highly oriented iodine-doped polyacetylene has been compared with that of ClO4-. These facts suggest that both interaction and localisation play dominant roles in determining conductivity at low temperature in metallic polyacetylene. cis-segments within trans-chains and impurities. inhomogeneities)..1 Disorder It is known that disorder is an inherent feature of polymeric systems. crosslinks.and FeCl3-doped polyacetylene and it has been found that a positive TCR in conducting polymers is highly influenced by the extent of disorder present in the sample [64]. chain termination. static fluctuations in the conformation of chain along its length are spread over some distance. the degree of doping. and the distribution and nature of dopant ions. 14 . Park and co-workers have found a metallic positive TCR at low temperature in ClO4--doped polyacetylene [63]. strong disorder. Chemical defects such as non conjugated carbon atoms inserted in the chain or impurities may result in localised and strong potential. sp3 defects. Recently. Both types of disorder may limit the conjugation length and hence the transport properties of polymers.5. Similar T1/2 dependence was found in the case of Naarman polyacetylene [67].

[73]. the effect of spatial disorder and anisotropy on the mobility of charge carriers has been reported using a dynamical Monte Carlo simulation. the doping process is inhomogeneous and the distribution of dopant ions in the 15 . The random interchain coupling changes the properties of the band gap to a pseudo gap. systematic investigation of the physical properties by controlling and varying different types of disorder has not been accomplished yet. It is found that small disorder decreases the mobility of low external fields whereas a considerable increase in mobility is found when spatial disorder reaches value about 5%. Harigaya and co-workers have reviewed the doping induced disorder in conducting polymers. Such studies are essential to optimise the performance of devices using these materials. 1. The rotation of rings or bonds owing to geometrical fluctuation is another disorder and has been shown to reduce the conjugation length [70]. A model was proposed by Levy and co-workers for understanding the experimental features observed due to disorder near the M-I transition in a q-1D conducting polymer. Both theoretical and experimental studies suggest that it is difficult to reduce the Peierls gap to zero without taking account of the effects of disorder [72]. disorder is detrimental to transport phenomena in solids.5. Therefore. The polymer is modelled as a composite medium consisting of spherical regions of ordered polymers. in general. the polymer chains are highly oriented. The perfectly dimerised Peierls ground state breaks down towards a ‘metal-like’ state at a critical random distribution of interchain coupling. but the axis of orientation varies randomly from sphere to sphere [74]. Within each spherical region. the charge is injected or removed from the polymer chain and dopant ions sit in the polymer matrix in order to maintain charge neutrality. Although a considerable amount of work has been devoted to investigating the role of disorder in transport properties. more extensive studies are required in order to understand the effect of different types of disorder on structural. They showed that dimerisation decreases and the density of states in the gap increases as a function of increasing disorder in interchain coupling. with a small but non zero density of states. randomly distributed in a much more disordered polymer host. The higher the disorder. or trap it. In general. the lower will be the dimensionality of the system. electronic and transport properties of conducting polymers. It can be concluded that. The main problem in understanding the conduction mechanism pertains to the correlation of disorder with that of the charge carrier transport. Lately.2 Doping During the doping process. The effect of disorder in interchain hopping has been investigated by Wolf and Fesser [71]. It has been argued in literature that disorder can either act as a barrier to the quasi-particle movement.Charge Transport in Conjugated Polymers Several studies on the effect of the disorder have been based on either the Huckel or SuSchrieffer-Heeger model with perturbation added in the form of either a screened coulomb potential representing a charge impurity or a completely localised potential acting on a single site [69].

doped polymers can be described within an idealised π-electron model with variable electron density.3-0.1 eV with five to seven carbon atoms in another chain that is in contact with a common dopant column. 16 . neglecting the effect of impurity potentials arising out of dopant ions is a drastic assumption because random weak potential can sometimes produce bound states in one dimension. the dopant ions have a negligible effect on the electronic properties of the system. Conversely. then the gap is enhanced. It has also been reported that the electronic gap between a soliton and the conduction band is decreased due to coulomb potential of the dopant ions and vanishes at a sufficiently high dopant concentration. Yamashiro and co-workers have estimated the dopant-chain interaction and its role in interchain transfer [82].17 eV and 0. the dopant may act as a bridge for the interchain transport. respectively.Handbook of Polymers in Electronics polymer matrix is not uniform. 76]. The aggregation of dopants into an ordered structure suggests that finite metallic segments exist which increase in length upon doping.10 eV. The interchain transfer via dopants has little effect on interchain states but yields a modification of the orbital energy spectrum. Cohen and Glick found that in the neighbourhood of a dopant ion the intrachain hopping is enhanced by 10% and the interchain hopping is enhanced by 100% [79]. They showed that the dopants mediate the largest interchain transfer of about 0. The electron spin resonance (ESR) measurements in conducting polymers studied by Bernier and co-workers have demonstrated that the dopants play a major role in the charge transport process [80]. This is mainly due to the complex morphology of the polymer matrix. It is suggested that a minor change in the arrangement of counterions relative to the polymer chain is capable of influencing the energy gap of the polymer lattice. after which they slowly migrate into the crystalline regions. If the position of the soliton is taken as centre. the density of states increases smoothly as a function of dopant concentration. However. which consists of both crystalline and amorphous regions [75. then it is observed that if counterions are located near to odd and even sites. As a result. The dopants easily diffuse into the vacancies in the amorphous region till saturation level is reached. Salkola and Kivelson suggest that the counterions affect the energy gap [81]. Taking this fact into account. Increase in dopant concentration beyond a critical level leads to the formation of a superlattice in many doped polymers [83]. after adding or removing electrons to a chain. Thus. According to the Kivelson and Heeger model [77]. The interchain hopping strength at sites in the presence and absence of dopant ions are estimated to be nearly 0. The influence of dopant ions on interchain coupling may either weaken it by placing chains farther away or vice versa. if the counterions are located near to even or odd sites then the gap is reduced. A theoretical study has revealed that disorder effectively quenches the Peierls distortion [78]. This has been attributed to high conductivity within the metallic regions and their weak dependence on the dopant species. A random distribution of dopants can have a strong effect on disordering.

in real materials. it has been argued that interchain coupling can be detrimental to polarons and bipolarons [86]. In an anisotropic Landau-Ginzberg model. being isotropic in nature. The role of interchain interaction in the case of oriented trans-polyacetylene has been investigated extensively by Leising and co-workers [88. the domain walls (kink/solitons) connecting the two degenerate bond alteration regions will always be generated by thermal fluctuations at finite temperatures and even a small density of these kinks will destroy the long-range order in one dimension. Bipolarons are stable with respect to transverse delocalisation as long as coulombic effects are negligible. Nevertheless.3 Interchain Coupling In contrast to the extensive efforts devoted to the studies of a one-dimensional model of π-conjugated polymers. t⊥ and t// being the interchain and on-chain transfer integral. a small t is sufficient to destabilise the polaron. which is the ratio of electron-phonon coupling to the electronic intersite coupling. t. This helps in determining the magnitude of the band structure anisotropy. It is found that a polaron is destablised and charge is spread over the whole crystal if the energy gained by the lattice relaxation of a single chain is of the order of 4t. in an infinite idealised one-dimensional polymer material. The interchain couplings have considerable influence on major sources affecting the solid state of polymers and thereby lead to substantial differences between the exact form of conducting polymers and their oligomers.Charge Transport in Conjugated Polymers 1. which is different from the general magnetic polaron (q=±e. no attention has been paid to account for the effect of the three dimensions of the real materials. Their study has shown that for a highly conducting polymer there is no gap around the Fermi energy consistent with the metallic properties of polymers. It has been found that the threedimensional effect dominates if t⊥/t// > 10-2 [84]. only nearest neighbour interactions are taken into account. Generally. Ab initio calculations in crystalline polyacetylene also confirm the possibility of instability of polarons and bipolarons [87]. respectively. The effect of interchain coupling on excitation has been studied by Shi-Jie using a tight-binding model [90]. A new spinless charged polaronic excitation (q=±e. Three-dimensional coupling is characterised by the transfer integral. Moreover. even a weak interchain coupling is sufficient to sustain the long ranges order up to a certain temperature. s=0) was obtained due to the transverse interchain coupling. s=1/2) obtained in the perfect 1-D 17 . can be expressed as the ratio of t⊥ to t//. Another parameter. Since the polaron binding energy is small. bond alteration can exist in the ground state. so only one or two transfer integrals are relevant. Three-dimensional band calculations performed on trans-polyacetylene and polyphenylvinylene yield similar results if t⊥/t// is at least 3 x 10-2 [85]. tanisotropy. For example.5. The result is confirmed by theoretical calculations with the Su-Schrieffer-Heeger (SSH) model. but it does not persist at finite temperatures. 89].

solitons and bipolarons have a major role in these systems [36. interchain coupling decreases the energy of creation of a polaron. Prigodin and Efetov have developed a theoretical model for interchain interaction at the M-I transition in a random network of coupled metallic chains [94]. The effect of interchain coupling on the electronic structure of both doped and undoped trans-polyacetylene has been studied by Conwell and co-workers [91]. The M-I transition in such a system is determined by the critical concentration of interchain crosslinks.6 Models of Charge Transport in Conducting Polymers As discussed in previous sections. It is proposed that non linear defects such as polarons. inhomogeneities often dominated the transport properties. In this model. the interchain coupling plays a significant role in charge delocalisation. decreasing at a constant rate from a maximum value at the bottom of the valence band. Additionally. In spite of innumerable theoretical and experimental work. screening and coulomb interaction and thereby determines the nature and stability of intrinsic excitations. a quantitative estimation of the effect of interchain coupling on transport properties of various polymeric systems has not yet emerged. They suggested that the interchain coupling is energy dependent. the interchain coupling is sufficient to shrink the energy gap between the soliton band and the conduction band to zero. 1. Although. in reality the coulomb interaction with dopant ions plays a significant role in giving rise to the metallic density of states. The detailed theoretical modelling is carried out only for transpolyacetylene and it should be extended to other polymeric systems in order to delineate a comprehensive picture about the effect of interchain interaction in both doped and undoped conjugated polymers [92. Recently. A polaron is more easily stimulated energetically in a longer chain than in a shorter one. The transport properties of conducting polymers are highly dependent on the way the chains are organised and arranged with respect to each other. the mechanisms for the formation of metallic state and charge conduction in conducting polymers have been the subject of intensive study since the occurrence of an insulator to metal transition was reported upon doping.Handbook of Polymers in Electronics model. which in turn depends on the localisation lengths and interchain coupling. In earlier synthesised conducting polymers. the interchain disorder due to intrinsic defects and the randomness in the distribution of interchain contacts induce localisation. As mentioned above. 95-97]. a metallic state can exist in such a random network of coupled metallic chains only if the concentration of interfibril contacts is large enough to overcome the percolation threshold. and metallic island models were proposed to 18 . Moreover. They suggested that the interchain interaction by itself is not enough for transport into the metallic state in doped conducting polymer samples. in principle. 93].

99]. More recently. In spite of the rapid progress in observing high quality samples of conducting polymers. the connection between the measured conductivity and structural parameters of the sample has to be sorted out. Improved homogeneity and a reduced degree of disorder in new kinds of polymers have provided a new opportunity for investigating metallic features through transport and optical measurements [49]. For example. Firstly. experimental results obtained in polyaniline and polyaniline derivatives were interpreted by invoking a q-1D variable range hopping model of Nakhmedov. In Kivelson’s model [100. The Kivelson model pertains to a phonon assisted hopping between soliton states in the case of lightly doped polyacetylene [100. electron hopping between solitons is a less strongly activated conduction mechanism and it is a dominant process at low temperatures (Figure 1. Chance and co-workers proposed interchain hopping for spinless conductivity in doped polyacetylene. σ=T9. However. 106]. At low temperatures. which is close to that observed experimentally. Secondly. charged soliton movement is difficult. especially in the case of iodine-doped polyacetylene [104]. The conductivity versus temperature data can be explained reasonably well in terms of the variable-range hopping (VRH) model.Charge Transport in Conjugated Polymers explain such features. Prigodin and Samukhin [98. Most of the transport measurements in such conducting polymers were in the insulating regime. the difference between microscopic and macroscopic transport properties has to be understood clearly. recent advances in synthesising ordered and highly conducting polymers have signalled the onset of a new generation of polymers [57]. the activation energy for phonon-assisted hopping or transition of an electron from the charged soliton to the neutral soliton is small if the neutral soliton happens to be near another impurity. doped poly(p-phenylene) and other doped polymers [102]. polarons and bipolarons in the charge transport is not very clear. it is suggested that the low-energy charge excitations introduced into polyacetylene by light doping are charged solitons because of the large binding energy. At reasonable temperatures the population of solitons is extremely small and consequently thermally activated conduction due to free. The mechanism accounts for the observed dopant concentration dependence of the conductivity in trans-polyacetylene and the observation of anomalously 19 . Thirdly. Kivelson’s model predicts a steep power law dependence for the conductivity.8a). Because of the disorder (namely the random distribution of impurities). The hopping conductivity is determined by the rate at which an electron hops between a pair of solitons. with interchain hops. the conduction pathways are essentially three-dimensional. However. The present section deals with the various models reported so far in addressing these problems. 101]. 103]. 101]. the role of solitons. the interpretation of experimental data in the framework of alternative models cannot be ruled out [102. the subtle details of the mechanism of charge transport are not yet understood. Similar to Kivelson’s model. The temperature and frequency dependence of conductivity is found to be in agreement with VRH among soliton-like states in the lightly doped regime [105.

this model does not explain the transition from spinless carriers to carriers with spins upon doping. Pietronero suggested that the main contribution to resistivity in conjugated polymers is due to scattering between the conduction electron and the phonon of the conjugated polymer chains [107].Handbook of Polymers in Electronics Figure 1.2 eV for 20 .8 Interchain transport of solitons and bipolarons in (a) polyacetylene and (b) poly(p-phenylene) low magnetic susceptibilities in the highly conducting regimes of several doped polymers (Figure 1. However. The observed high conductivity of heavily doped polyacetylene has been explained using the one-dimensional model.8b). The only possible scattering for polymers is from kF (the fermi vector) to –kF or vice versa involving large momentum (2k F) phonons of high energy (h ν~0.

High-order scattering processes with low energy phonons may then become less important. because of phonon freezing effects.Charge Transport in Conjugated Polymers polyacetylene-type systems). At 0. All the above factors suggest that in high-quality conducting polymers the electronic mean free path could be much larger than the structural coherence length and real metallic features could be observed. The possible limits for the conductivity arise from the chain interruptions and/or phonon scattering. However. They described the expression for the conductivity as: 2πnν0e 2a 2t0 α h 2 2 2 ⎛ hν ⎞ exp⎜ ⎟ ⎝ kBT ⎠ (1. the resistivity is very small at low temperatures. t⊥ ~0. Even a small interchain coupling. This value increases exponentially at low temperatures. hν0 >> kBT. In the case of elastic scattering (kBT >> hν).1 eV. where kB is the Boltzmann constant. When the concentration of chain interruptions is sufficiently high such that the left hand side of equation 1. may give rise to the suppression of the Peierls distortion.4 x 107 S cm-1. As discussed earlier. and a small number of phonons gives the conductivity at room temperature as 107 S cm-1. the interchain couplings are necessary to prevent 1D localisation.12 eV. t0 is the electron hopping matrix element [107].3 is small. At room temperature this analysis gives high intrinsic conductivity. 21 . σ = 1.e. h is Planck’s constant. with a rapid rise when the thermal energy kBT approaches the energy of the 2kF phonons. in polymers. ν0 is the phonon frequency. The condition necessary for the system to remain three-dimensional is L/a >> 2t0/t⊥ (1. Since these phonons are thermally excited only at higher temperatures.6 x 105 S cm-1 which is nearly an order of magnitude less than the value estimated for graphite intercalation compounds.3) where α (~4.1 eV/Å) is the electron-phonon coupling constant. This is because phonons of wave vector 2kF are required to backscatter electrons. Since the charged ions are spatially removed from the q-1D conduction path. the rapid increase in resistivity can account for the change to metallic temperature dependence. then the wave function will be localised. i. n is the conduction electron density and a is the C-C distance in the chain direction. A large t0.4) where L characterises the distance between the chain interruptions or sp3 defects or crosslinks. the electrical conductivity is estimated as 1. With first-order scattering one obtains a strong conductivity increase even at room temperature. Kivelson and Heeger carried out a detailed study on the intrinsic conductivity of conducting polymers [77]. which is a prominent feature of the conductivity in conducting polymers.. the usual scattering of phonons is reduced. only 2kF phonons scatter. this estimation is not realistic since.

the temperature dependence of conductivity gradually varies from 1D behaviour at high temperatures to that of an isotropic 3D behaviour at low temperatures. which consists of partially crystalline and amorphous regions. The charge carriers are subjected to 1D localisation while passing through the amorphous region in between the crystalline region and thereby the movement of charge carriers occurs through the 1D localised regions and often dominates throughout the 3D extended states in crystalline regions. which is expected to be highly anisotropic [110-112]. suggesting that the effect of finite temperature emerges through phonon scattering. Microscopic properties in crystalline and amorphous regions are different and hence the usual Anderson localisation in the homogeneous disorder limit is not appropriate for conducting polymers. 115]. More recently. They set the cut-off temperature regimes in which band transport crosses over to hopping transport. t⊥~0. σdc ∝ exp-(T1/T)1/2. the band transport is governed by phonon scattering and disorder while at low temperatures. Conducting polymers were considered as an inhomogeneous system. According to their model. 109]. the VRH conductivity obeys a q-1D Mott’s law. τ being the scattering time. the temperature dependence of conductivity shows a power law behaviour. Therefore.3/τ. Later. When the volume fraction of 3D extended states increases. The overlap of π-orbitals gives rise to crystalline regions whereas amorphous regions emerge from weak chain interactions. the probability of movement of charge carriers is through the path of least resistance and therefore. but 22 . Nakhmdeov and co-workers carried out a study of hopping transport in q-1D systems near the M-I transition with weak disorder [98]. In a high temperature regime. an abrupt transmission from extended to localised states is expected at the critical interchain exchange integral t⊥c~(3h/2πτ). the hopping has been ascribed to Mott’s VRH. Moreover. In these cases. the delocalisation in a q-1D metallic chain appears only if t⊥ is larger than the threshold value. the conductivity follows exp(-T0/2T)exp[-(T0/2T)]1/2 dependence. the conductivity versus temperature curve exhibits a characteristic maximum at temperatures where the phonon backward scattering time becomes comparable with the impurity scattering time. It is found that at low temperatures. In the intermediate range. these temperature regions are different in a q-1D system when there is a weak intrachain coupling. Epstein and co-workers have widely used q-1D models to interpret transport properties in both metallic and insulating polymer systems [113. the system is expected to undergo a transition from insulator to metal.Handbook of Polymers in Electronics Similar charge transport models have been proposed by Prigodin and Firsov [108. Joo and coworkers extended this model. The role of phonon forward scattering is to break the phase coherence of the impurity scattering and thereby destroy the weak localisation. a percolative metallic transport is expected. When the size and volume fraction of the crystalline region increases with respect to the amorphous region. However. Samukhin and co-workers proposed [99] a q-1D fractals model in order to explain the experimental data obtained for poorly conducting polymers. In the intermediate temperature region.

is decreased below the experimentally observed temperature range (over which the above equation holds) if the metallic islands correspond to 3D bundles of the polymer strands.Charge Transport in Conjugated Polymers the characteristic temperature T1 is greater than T0 for a 1D chain by a factor 1/D-1. 118] and polymers filled with carbon black or alumina flakes.3 with the presence of an insulating layer surrounding each island above the percolation threshold. Similar temperature dependence was obtained for dc conductivity. Sheng’s fluctuation induced tunnelling (FIT) model was used extensively to interpret transport properties in metallic polymers. the doping dependence of T0. Experimental measurements of TEM. thermally activated voltage fluctuations across the junction. A temperature range. electron paramagnetic resonance (EPR) spectroscopy and magnetic susceptibility studies also suggest that pristine and doped polyaniline contain at least two types of spin carriers. The size of these islands is estimated to be 200-300 Å. the voltage fluctuations directly influence the tunneling probability and introduce a characteristic temperature variation to the normally temperature independent tunnelling conductivity. D being the dimensionality of the system. Qiming and co-workers proposed a granular-rod model for the metallic state of the conducting polymer [116]. The electrical conduction is dominated by electron transfer between large conducting segments. x [120]. The macroscopic conductivity results from anisotropic threedimensional VRH in the network of metallic rods. It was suggested by Conwell and Mizes that the 23 . the relevant tunnel junctions are usually small in size and are therefore subject to large. each cluster being very dense and well isolated. the anomalous 1/T dependence of the thermoelectric power as well as the linear increase of Pauli susceptibility with dopant concentration. This model was originally developed for granular metal [117. The polymer system is described in terms of highly conducting regions separated by much less conducting or insulating areas. σ = σ0exp(-T0/T1/2). X-ray diffraction (XRD). the conductivity behaviour is similar to that of a granular metal and this data fits transport via charging energy limited tunnelling between conductivity islands. For all compositions. At no composition level does the conductivity appear truly metallic. Since the electrons tend to tunnel between conducting regions at points of their closest approach. By modulating the potential barrier. temperature dependence of dc conductivity and magnetic susceptibility indicate the applicability of this model. In this model. the metallic islands correspond to single strands of polymer. The data were found to be consistent with percolation among these islands for x ≥ 0. A non metallic feature of doped polyacetylene was explained in the framework of this model [119]. This model explains very well the temperature dependence of the conductivity. However. In contrast to q-1D models. Low frequency conductivity is entirely controlled by the weak charge transfer between clusters. where the variable range hopping is valid. A similar model was used to interpret the transport properties of emeraldine polymer as a function of the protonation level. Lux and co-workers reported scanning electron microscopy (SEM) and transmission electron microscopy (TEM) pictures of highly conducting polyaniline in support of the conducting island concepts [121].

In contrast to conductivity. while for diffusive motion t⊥τ// is much less than h/2π. hopping/ tunnelling transport and 3D disordered metallic transport (Figure 1. the thermoelectric power could then follow the intrinsic metallic behaviour. Paasch was of the opinion that this model contains seven independent data and so may describe 24 . a parallel phonon assisted hopping transport was included in the Kaiser and Graham model. Also. In addition to the tunnelling transport across the insulating barrier. Such barriers could be due to material imperfections that dominate the total resistance of the sample [48]. and defects in the metallic regions are not considered in the FIT model. the issue of transport in highly oriented metallic conducting polymers is still debatable. However.6 x 10-19 C). experimental results demonstrated by Park and coworkers [124] indicate that σ// /σ⊥ increases with σ// and therefore.Handbook of Polymers in Electronics conduction mechanism is not due to FIT dependence in conducting polymers since the metallic regions in the FIT model have negligible temperature dependence of conductivity. then σ⊥ is the mixture of band motion and hopping. They showed that for band motion t⊥τ// is much greater than h/2π. n = 1022 cm-3. The bulk conductivity is the combination of Kivelson and Heeger q-1D transport. The linear thermoelectric power behaviour observed indicates a smaller interaction between electrons and phonons than in normal metals. the phonon scattering. if σ~105 S cm-1. their contribution to thermoelectric power) will be small [126]. if the barriers are reasonably good heat conductors. 123]. τ// being the average time for the electron scattering along the chains (τ//~10-14 s from σ// = ne2τ//m*.1 x 10-28 g. If the intrinsic conductivity is very large and barriers form only short segments in the conduction path. Furthermore. Voit and Buttner examined the FIT model critically and it was concluded that physical parameters obtained from this model do not allow consistent description of highly doped polyacetylene [125]. m* = free electron mass = 9. These could be due to charging energy effects in interchain transfer at low temperatures or to quantum corrections.9). This heterogeneous model was reviewed by Kaiser for understanding the experimental data obtained on Naarman-polyacetylene. In contrast. They determined the band motion versus diffusive hopping transport in oriented metallic conducting polymers to understand the effective dimensionality of the system. which is consistent with the remarkably high conductivities observed [127]. the measurements σ// /σ⊥ as a function of temperature in oriented metallic trans-polyacetylene shows that σ// /σ⊥ is nearly temperature independent and hence it is impossible that σ⊥ is due to diffusive hopping in both cases [122. Localisation effects can appear at low temperatures despite the high conductivity. If the system consists of high conducting regions mixed with low conducting regions. but the magnitude is very much larger than the barrier conductivity due to geometrical factors. scattering due to imperfections. the temperature differences across them (and therefore. Kaiser and Graham extended the FIT model for heterogeneous systems by introducing geometric factors to the insulating barriers. the temperature dependence of the measured conductivity reflects that of the barriers. e = 1.

Moreover. However. The transition of polymer system from q-1D to 3D was studied as a function of doping level [132]. Schreiber and Grussbach [131] suggested that the fluctuations in mesoscopic systems could give a wide range of values of the exponent due to the fractal nature of wavefunctions near the mobility edge. 25 . He modified the FIT model.Charge Transport in Conjugated Polymers Figure 1. 129. These segments exhibit a dimerisation gap which acts as a tunnelling barrier for the charge carriers. The exponential dependence of conductivity in the insulating regime of conducting polymers has been usually attributed to VRH. He argued that multiparameter fits of simple dependencies sometimes make the picture seem unambiguous whether the relative influences of the different contributions are reliable or not [128]. In general. 130].9 Schematic representation of the conduction processes in (a) microscopic or (b) macroscopic pictures that are in agreement with transport data in Naarman-polyacetylene the smooth temperature dependence. T–1/2 behaviour of conductivity is often observed in granular metallic systems. however. arguing that one of the main barriers for the tunneling process is the chain segments with residual dimerisation. a wide range of exponent (d = 0.25-1) has been observed [49. the multiple parameter fitting procedure in FIT model has not been found satisfactory to explain the physical properties of conducting polymers.

134] reported that the enhancement in interchain interaction with increased dopant concentration can induce 3D localisation of the electronic states. A RDM analysis on poly(p-phenylene) also indicates the presence of a set of conducting states in the vicinity of the band edge. that the charging energy is the principal barrier to hopping. Phillips and co-workers proposed a random dimmer model (RDM) [137-139] which has a set of delocalised conducting states. 26 . Zuppiroli and co-workers have proposed a model which describes adiabatically. It was shown that the electron transport in these materials is due to correlated hopping between polaronic clusters. that initially allow a localised particle to move through the lattice almost ballistically. even in 1D. therefore. Schon and co-workers suggested the possibility of band-like transport in oligothiophene as a result of strong observed dispersion of the valence band based on band structure calculations [136]. the dimensionality. He showed that the most relevant parameter for causing localisation in the number of chain interruptions is the number of chain interruptions and not the channel length. crosslinking between chains. if the interchain hopping term is equal to the interchain hopping strength (3D case) or if the number of channels is very small (1D case). therefore. etc. He used the many-channel Buttiker-Landaur conductance formula [135] to study the conductance as a function of length of the system. Recently. the critical chain length for which the conductance begins to drop should be used to characterise the transition between diffusive and non diffusive conductance. They showed. The final temperature dependence is the same as in the case of models of Sheng. such as polyaniline and heavily doped polyacetylene. 143].Handbook of Polymers in Electronics Stafstrom [133. the q-1D nature of conjugated polymeric systems provides an example of a class of materials that differ from previously studied materials in the way the conductance responds to disorder in the form of chain interruptions. the usual type of disorder-induced exponentially localised wave functions appear. coulomb interactions and multi-phonon character in the framework of hopping conduction [142. 141]. Moreover. both theoretically and experimentally. Each channel contains several polymer segments represented by chain interruptions. The hopping across such a chain interruption should. The chain interruptions along the channels can be caused by sp3 defects. In highly disordered conducting polymers. The conductance of the system is unaffected by the presence of chain interruptions up to a critical value and. Polaronic clusters which originate from fluctuations in the dopant concentration function as metallic grains in the granular metal hopping model. Therefore. Calculations performed on polyaniline demonstrate explicitly that the conducting state of the RDM is coincident with a recent calculation of the location of the Fermi level in the metallic region [140. The model is found to be applicable to the M-I transition in a wide class of conducting polymers. the usual exponential dependence of temperature is explained by phonon assisted hopping or tunnelling or both. They showed that any disordered bipolaron lattice can be mapped onto a RDM. be reduced considerably compared to the interchain hopping. homogeneity.

Nevertheless. 145]. According to this model. 27 . Moreover. coulomb interaction.. On the other hand. None of the models for charge transport in these polymers is able to explain all the features of the conducting polymers. Arie or Efros and Shklovskii [144. The major hurdle is in quantifying the intrinsic and extrinsic parameters. in this model the localised states correspond to the Urbach states in amorphous systems since the optical absorption from a distribution of states extend out from the fundamental absorption band edge. and electronlattice coupling tends to broaden and reorganise the energy levels at each site. the theoretical understanding of charge transport phenomenon is not yet completely developed in these polymers. interchain processes are more important and determine the transport mechanism. better understanding of the charge transport in these materials is essential to determine the various physical phenomena operating in the polymerbased electronic devices. the theoretical work by Ovchinnikov and Pronin [147] and Lewis [148] are slightly different from other models.7 Conclusions It can be concluded that interchain interaction and disorder play a leading role in governing the transport properties of polymers. Such a carrier can detrap by an activated process and diffuse along the chain. Both regimes described by the model reproduce the experimental results in a remarkable way. frequency and temperature dependences of charge transport in both conducting and non conducting polymers. Nagashima and co-workers recently described ac transport studies in polymers by using a statistical model of resistor network [146]. interchain and intrachain interaction. for example. Thus. The model takes into account the polydispersiveness of the material as well as intrachain and interchain charge transport processes. etc. conduction by percolation is possible in such a system if an infinite cluster of chains can be connected by impurity centres. At low frequencies. They estimated the electric field. Therefore.Charge Transport in Conjugated Polymers Abeles. at high frequencies charge transport should be restricted along the polymer chains. electron-phonon interaction. extent of conjugation length and disorder. In the former model. 1. Lewis and co-workers suggested that the charge transport occurs by tunnel transitions between localised states and lattice fluctuations. as interchain processes should be dominant. whose contributions to charge transport are greatly intermixed. a q-1D percolation model was proposed for explaining the conductivity. This polaron can recombine with another impurity centre near the chain and then escape to an arbitrary chain adjacent to the second impurity centre. charge delocalisation. an impurity captures an electron from one of the adjacent chains and forms a charged impurity centre. Among various models proposed by several researchers for conducting polymers in the insulating side. The real and imaginary part of the resistivity was determined using a transfer-matrix technique.

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Advanced Physics. O. Synthetic Metals. Physical Review B. 51. 142. Reedijk. O. 115. Roth in Hopping Transport in Solids. 140.H. Schreiber and H. 141. 377 and references therein. 67.F.S. 7. 101. Synthetic Metals. 1995. Shklovskii. Solid State Communications. 252. 1990. M. Martens. Pollak.B. D. S. B. 1233. Chauvet. S. 1992. D. 1994.A. R. P. 63. L. dos Santos. 131. B. 1985. Zuppiroli.A. Buttner. Laks.S. 63.M.A. Kaiser. G. Kloc.B. NorthHolland. C. van Bohemen. Chauvet and L. 1993. J. Stafstrom. 1992. Forro.B. B. Bleier. P. Zuppiroli. A.Charge Transport in Conjugated Polymers 125. Caldas. 65. H.P. A.J. Wu. 385. Kaiser. Physical Review Letters. Grussbach. 133. B. D. C. 1995. Paasch. J. 115. S. Synthetic Metals. 40. S.A.J. 50. 135. Buttiker. 143. 31. B65. O. 88. Galvao. 2806. Forro. 137.P. Stafstrom.C. Wu and P.C.. 127. dos Santos. H-L. Imry. D. 527. Batolgg. P. Bujard. 44. Amsterdam. 1990. 75. Michels.W. K.H. 65. Kai and W. Brom and M. 35 . Wernet. 130. Y. Phillips. 1991. 134. Phillips. 786. Synthetic Metals. 1805. Physical Review B. Schon. Hilt. 126. 1989. Physical Review B. Dunlap. 475. 115. M. Paschen. Galvao. J. 1994. Philosophical Magazine. 1989. 185.N. S. H. D. Eds. Roth and H. de Melo and M. Physical Review B. L. 1985. 707. 138. Ch. de Melo and M. Physical Review Letters.L. M. S. Pinhas. Synthetic Metals. 1991. 51. 2000. 5196. Caldas. 129. 6201. Annual Review Physical Chemistry. 183. Physical Review Letters. 4137. S. 139. 45. 136. 1994. 65. 128. 1999. Science.J. Synthetic Metals. Laks. 36. Phillips and H. L. Landauer and S. Bussac. Paschen. M. 1988. 132. Voit and H.

148. Sheng. Faraday Discussions Chemical Society. Pronin. A.J. Sklovskii. 147.I. T. 88. Nagashima.A. 41-43. B. 36 .N. Arie. A. R. 1973. 8. 905. Faria. Lewis. 31. 146.N.Handbook of Polymers in Electronics 144. 1975.L. 145. 3373. 1989. P.M. H. Ovchinnikov and K. Physical Review B. 1999. Synthetic Metals.A. 59. Physical Review Letters. 1991. Journal of Physics C. Abeles and Y. Efros and B. 44. L49. Onody and R. 189.

In first-generation conducting polymers (1976-1986). The π-electrons are highly delocalised and easily polarisable. the maximum possible values of electrical conductivity were limited due to the presence of structural and morphological disorder. the intrinsic q-1D nature and the extent of both intra.and interchain delocalisation of π-electrons play significant roles in the structural. and the enhancement of conductivity in doped polyacetylene. conjugated polymers. the conjugation length. as a result the π-electrons were not very well delocalised to facilitate intra. and these features play important roles in the electrical and optical properties of polyconjugated systems. It also makes the latter rather different from conventional electronic systems [6-8]. (CH)x. poly(p-phenylenevinylene) (PPV). 37 . The polyconjugated chains -(C=C-C=C-C=C)n. carbon nanotubes. plays a crucial role in the physical properties. significant improvement in reducing the structural and morphological disorder has helped to create the new generation of conducting polymers in which the metallic features are predominantly observed in transport measurements. In the past decade. PANI. The electrical and optical properties of (CH)x. disorder-induced localisation. PT. by several orders of magnitude [4. 5]. in iodine-doped Tsukomoto (CH)x. etc. Nevertheless. the conductivity was around 105 S cm-1 [11]. 9]. electrical and optical properties of polyconjugated systems.1 Introduction In the past three decades. Moreover. In general. are some of the wellknown π-electron systems. For example. several types of π-electron systems have shown very interesting features in electrical transport properties [1-4].and interchain charge transport [10]. the complex morphology of polymeric systems. [SN]x. PPy. Polymeric materials were considered as insulators before the discovery of metallic poly(sulfur nitride). Menon 2.2 Electrical Properties of Doped Conjugated Polymers R. which are partially crystalline and partially amorphous in nature. the strength of the interchain interaction and the extent of disorder are some of the significant parameters that govern the physical properties of polyconjugated systems. carbon-60. PPP and polythienylene vinylene (PTV) are some of the extensively studied conjugated polymers [7. Charge-transfer complexes.consist of alternating single (σ-bonds) and double bonds (π-bonds). The metallic features were rather weak.. etc. This was mainly due to the presence of strong structural and morphological disorder. intercalated graphite.

interchain interaction and doping level [18. the chains are extended. interchain interactions. and this is largely due to the presence of strong disorder in polymeric systems. and its temperature dependence showed a significant metallic positive TCR in the range 150-350 K [14-16]. In degenerate systems like (CH)x.8 to 4 eV [9]. In fibrillar morphology. several groups had started making high quality materials of PPV. solitons. by orienting the polymer chains by mechanical stretching it is possible to enhance the conductivity along the orienting axis. 20]. as the interchain interactions and the carrier density increases and the extent of disorder decreases. In conducting polymers the doping process can generate various types of charge carriers like polarons. these excitations could behave more like free carriers. hence it is possible to have delocalised states along the chain length direction. morphological and doping induced defects. The charge carrier density in conducting polymers can be varied by several orders of magnitude (nearly 8 orders) by doping. solitons are formed. The band gaps of known polyconjugated systems vary from 0. The maximum level of doping in conjugated polymers could be as high as 50%. and this tends to localise the electronic states. hence it can be considered at the semiconductor-insulator boundary [18]. PANI and polyalkylthiophene (PAT) [9].. chain ends. etc.. and that corresponds to one dopant per two monomers. the chains are randomly dispersed and the physical properties are isotropic. the structure of the polyconjugated chain.. both polarons and bipolarons are formed depending upon the energetics. The conductivity was enhanced to 103 S cm-1 in the case of regioregular PAT [9. the conductivity was enhanced to nearly 500 S cm-1. voids. However. [9]. especially at doping levels below 6%. [7. The conductivity of undoped polyconjugated systems is 10-6-10-10 S cm-1. However. PT. disorder. oriented PPV samples the conductivity is of the order of 104 S cm-1 [12]. 8. etc. the conductivity is nearly 500 S cm-1 [13]. 8. etc. bipolarons. PF6-doped PPy and PT samples (prepared by low temperature electrochemical polymerisation).. In doped. With the development of counterion-induced processibility of PANI by dodecylbenzoyl sulfonic acid (DBSA) and camphor sulfonic acid (CSA) dopants. and an anisotropy of conductivity of the order of 100 can be 38 . 17]. PPy. In unoriented conducting polymer systems. chain entanglements. etc. In fully doped systems. the chains are coiled up. The carrier mobility in doped conducting polymers is much lower with respect to that in inorganic semiconductors. in non degenerate systems like PPy. The M-I transition in doped conducting polymers is mainly governed by the extent of disorder. 19]. free carriers.Handbook of Polymers in Electronics By the early 1990s. In globular morphology. Transient charge carriers can be generated by photoexcitation in conjugated polymers [7. and this to a large extent depends on the doping level. 19]. the carrier density could be as high as 1022/cm3. The main source of disorder in conducting polymers are the sp3 defects in the chain. However. In high quality.

2 Metallic State The metallic state in doped conducting polymers is inferred from the following: a large finite dc conductivity as the temperature (T) goes to 0 K. If Lc is greater than the average structural coherence length (which characterises the size of the crystalline regions). linear term in the specific heat at low temperatures. 39 . However. Since conducting polymers are partially crystalline and partially amorphous. The critical parameter in the M-I transition is the statistical average of a wide range of values of the correlation/localisation length. recently Park and co-workers reported a metallic positive TCR in doped (CH)x. free carrier absorption and large metallic reflectance in the infrared. This evidence indicates the presence of a continuous density of states with a well-defined Fermi energy. In some conducting polymers. This evidence indicates that in spite of the disordered q-1D nature of polymer chains. the interchain coupling can be sufficiently large to enable the formation of three-dimensional metals.5 K. temperature independent Pauli spin susceptibility down to 10 K. and in some others it was only below 20 K. Although conducting polymers are intrinsically q-1D electronic systems. the typical metallic positive TCR was observed from 300 to 150 K. linear temperature dependence of the thermoelectric power down to 10 K. the volume fraction of crystalline regions and the size of the crystalline coherence length play dominant roles in the charge transport. it is possible to have a metallic state in these systems [22]. which is quite exceptional [21]. Although the typical negative TCR in high quality conducting polymers is indicative of non metallic behaviour. etc. then the extent of disorder is considerably higher. σ. from 300 to 1. which means the system sees only an average of the random fluctuations of the disorder potentials.Electrical Properties of Doped Conjugated Polymers easily achieved. if Lc is less than the average structural coherence length. This implies a finite value of conductivity and a finite density of states at the Fermi level at very low temperatures.. respectively [9. (W = dlnσ/dlnT) has a positive temperature coefficient. hence the carrier transport is slightly hindered by the presence of disorder potentials in the amorphous region. then the disorder can be considered as within the weak limit. 2. In the metallic state. as expected in the case of disordered metallic systems. the disorderinduced localisation plays a dominant role in the M-I transition and in the transport properties of conducting polymers. its temperature dependence was rather weak so that the logarithmic derivative of conductivity. In general. the average size of the delocalised states is considerably larger than that of the structural coherence length. Lc. Conversely. The values of Lc and structural coherence length can be determined by transport property measurements and X-ray diffraction. 20]. [20].

Journal of Physics: Condensed Matter. Hence. the conductivity in the highly oriented state along the direction of the chain alignment is given. According to the Ioffe-Regel criterion.1 The details of various doped conducting polymers in the metallic state Polymer Polyacetylene Poly(p-phenylene vinylene) Polyaniline Polypyrrole Poly(3. relaxation time. Reproduced by permission from M. m. σ⎜⎜. 10. 31-33. and effective mass. The details about metallic conducting polymers are shown in Table 2.1) 40 . λ is around 10 Å. IOP Publishing. and kFλ ≈1-10. in a metallic system. the first-order scattering should induce a strong enhancement in conductivity in one-dimensional chains. τ.2. 32. The values give approximately the highest observed values. 7171. Moreover. due to phonon freezing effects. involving the high-energy 2kF phonons [27]. of the carrier (electrical conductivity.1 [26]. Menon. the interatomic distance is considered as the lower limit for the mean free path.4-ethylene dioxythiophene Poly(3-methyl thiophene) a b Abbreviation (CH)x PPV PANI PPy PEDOT PMeT Repeat Unit C2H2 (C6H4)C2H2 (C6H4)NH C5H2N C7H4O2S (C5H2S)CH3 Orientability High High Low Low Low Low Crystallinitya 80% 80% 50% 50% 40% 40% Conductivityb 104-105 104 400 400 300 400 Approximate values for high-quality samples. λ. In S cm-1. possible even at room temperature. where kFλ = [h(3π2)2/3] / (e2ρn1/3).1 Conductivity The electrical conductivity is mainly determined by the carrier density. where e is the electron charge). n ≈1021 per cm3. Table 2.Handbook of Polymers in Electronics 2. The conductivity in the chain direction. in a one-dimensional chain is given by: σ⎜⎜ = (ne2a/πh)vFτ = (ne2a2/πh) / (λ/a) (2. kF is the Fermi wavevector and ρ is the electrical resistivity [23-25]. 1998. In the cases of (CH)x and PPV. σ = ne2τ/m. n. In highly doped conducting polymers. at room temperature. Ahlskog. for a metallic system kFλ is greater than 1. Pietronero suggested that in a one-dimensional chain the only possible source of scattering for charge carriers is from +kF to –kF. R.

Since conductivity is directly related to the mean free path (which is rather sensitive to the presence of any disorder) the variation in low temperature conductivity is quite dramatic as disorder varies.4 K)/ρ(300 K)]. the sign of m is negative when γFσ > 8/9. W.e. Moreover. Hence. t0 (= 2-3 eV) is the π-electron hopping matrix element and τ is the backscattering lifetime. The low temperature conductivity measurement is a simple and sensitive method to get a qualitative level of understanding about the extent of disorder present in the system. ≈ 107 S cm-1. The second term in Equation 2. However. In disordered metals. and this results in the change of sign (from negative to positive) in the TCR at low temperatures. The conductivity in the disordered metallic regime is expressed by [25. p = 2 in the clean (weakly disordered) limit or 3/2 in the dirty (strongly disordered) limit). increases the temperature dependence of W gradually moves from a positive (metallic) to a negative (insulating) temperature coefficient at low temperatures. ρr [(= ρ(1.2) where m´ = α[4/3 – γ Fσ/2]. The approximate values of ρr for various conducting polymers in the metallic (M). vF (=2t0a/h) is the Fermi velocity. i.. the theoretical studies suggest that the intrinsic conductivity in one-dimensional models of conjugated polymers is expected to be even larger than that of conventional metals. Usually. p = 3. γFσ is the interaction parameter.2 results from the e-e interactions and the third term is the correction to σ(0) due to the localisation effects. for inelastic electron-electron (e-e) scattering. this ensures that there is a finite conductivity as T→0.Electrical Properties of Doped Conjugated Polymers where a is the carbon-carbon distance. 20]. p is determined by the scattering rate (for electron-phonon scattering. since the main scattering involved in a conducting polymer chain is only due to the 2kF phonons. In the limit of elastic scattering for a half-filled band system. another two orders of magnitude of enhancement in conductivity should be possible. and by including the inelastic scattering process below the characteristic temperature (kBT∼hω0/4 and T∼600 K). W = d(lnσ)/d(lnT) [29. critical (C) and insulating (I) regimes are shown in Table 2. In general.2 [30].e. 31] σ(T) = σ (0) + m´T1/2 + BTp/2 (2. as the resistivity ratio. α is a parameter depending on the diffusion coefficient. 41 .. σ⎜⎜(300 K)≈105 S cm-1. The characteristic behaviour of the temperature dependence of conductivity can be understood in detail by defining the reduced activation energy. If the system has a finite value of conductivity with a negative TCR. i. e-e interactions play an important role in the low temperature transport. In later models. Similar estimates of conductivity have also been obtained by the Kivelson and Heeger model [28]. then W shows a positive temperature coefficient at low temperatures. the conductivity is expected to increase exponentially at low temperatures. as the logarithmic derivative of the temperature dependence of conductivity.

and insulating regime (I) M C σ(300 K) >5. The stretchability and the maximum obtainable conductivity in I-(CH)x is very much dependent on the film thickness. the positive TCR was observed at temperatures above 150 K.J. are 150 and 50 Å. 20-22. (1. 1997. The data comes from samples with different degrees of orientation and therefore does not give an entirely consistent picture of the M-I transition in this system. although in earlier work the positive TCR was observed in FeCl3-(CH)x and PANI-CSA down to 180 K. Menon. The average crystalline coherence lengths. in both stretched and unstretched films. The conductivity for a ClO4-(CH)x sample at 300 K is nearly 40.3 states (eV C)-1. 32]. The conductivity is higher in thinner films (below 10 μm).3 K)/ρ(300 K)] of various conducting ρ polymers in the metallic (M). Iodine-doped polyacetylene I-(CH)x is one of the most extensively studied systems among doped conducting polymers [11. R.6-11.000 <2 x 104 <104 <100 <1. respectively.000 S cm-1.8 x 1018 states (J A S)-1). as shown in Figure 2.000 S cm-1. Recently Park and co-workers [21] have observed. Heeger.4 9.5 K. The maximum room temperature conductivity parallel to chain axis in highly oriented I-(CH)x is nearly 105 S cm-1. parallel and perpendicular to the chain axis. and the anisotropy of conductivity is 100-200. Journal of Physics: Condensed Matter. IOP Publishing. The density of states at the Fermi level is approximately 0.8-165 2.5 K. The structural and physical properties of I-(CH)x have been reviewed by Tsukamoto [11].2 The σ(300 K) and ρr ≈ [ρ(1.7-34 4. For samples with conductivity in the range 2. from 300 to 1. a metallic positive TCR. A. Ahlskog. In highly conducting samples. critical (C).400 4 x 10 -10 300-400 250-350 -1 3 1-2 x 104 100-300 1-4 x 10 3 200-300 200-250 Conductivity data is given in S cm .000-20.1. in ClO4-doped (CH)x.000 >5 x 10 4 a I σ(300 K) 3-5 x 104 2-5 x 10 4 ρr (CH)x-I2 (CH)x-I2 (CH)x-FeCl3 PPV-AsF5b PPV-H2SO4 PPy PANI a b ρr 10-20 9. Reproduced by permission from M. for the first time in conducting polymers. 9.Handbook of Polymers in Electronics Table 2. The room temperature conductivity of highly oriented I-(CH)x is nearly a factor of two 42 .7-27 2-10 2-5 4 ρr >20 >400 >27 >50 >60 >10 >10 σ(300 K) <3. 4145. the carrier density is nearly 1022 cm-3 and the mean free path is around 500 Å.000 <200 <200 <10 <5 <2 <2 <2 <2 <2 >2 x 104 300-2. Its conductivity increases by a factor of two at 1.

(Reproduced with permission from Y. Synthetic Metals. 33]. The W versus T plot of the ρ(T) is shown in Figure 2. and upon ageing it tends towards a negative temperature coefficient. Elsevier Science SA.W.41 x 10-5 (Ω cm). and it shows a large finite conductivity at temperatures below 1 K. Choi. ρ(300 K) ~ 5.1 Normalised resistivity (ρ) versus temperature for ClO4-doped polyacetylene samples doped by: (1) ClO4 (Fe). 96.01 x 10-5 (Ω cm).Electrical Properties of Doped Conjugated Polymers Figure 2. Suh.S. 1-3.84 x 10-5 (Ω cm). 81) larger than that of ClO4-(CH)x and FeCl3-(CH)x. The metallic samples have a rather weak negative TCR. The temperature dependence of resistivity of I-(CH)x samples is shown in Figure 2. as expected for insulating systems. (5) ClO4 (Cu). ρ(300 K) ~ 6. so that it continuously moves from the metallic to insulating regime. This indicates that the positive TCR in conducting polymers is quite sensitive to subtle variations in the extent of disorder present in the system.58 x 10-5 (Ω cm).S. ρ(300 K) ~ 5. (6) ClO4 (Cu). yet. E. (3) ClO4 (Fe).2b. The sample B2 is systematically aged up to B6. ρ(300 K) ~ 1. it does not show any metallic positive TCR [30]. 1998. Park. (2) ClO4 (Fe). (4) ClO4 (Fe). The metallic B2 shows the expected positive temperature coefficient of W(T).2a [30.67 x 10-4 (Ω cm). ρ(300 K) ~ 2. 43 . ρ(300 K) ~ 8. and D. The absence of a positive TCR in the case of I-(CH)x suggests that the doping induced disorder is higher with respect to that in ClO4(CH)x and FeCl3-(CH)x systems.88 x 10-5 (Ω cm).

the σ(T) below 4. both parallel and perpendicular to the chain axis in oriented I-(CH)x samples. The unstretched sample has a σ(300 K) ∼ 800 S cm-1.2 (a) Resistivity versus temperature for an iodine-doped polyacetylene sample aged from metallic B2 to insulating B6. As described in previous works [18.Handbook of Polymers in Electronics Figure 2. The T1/2 dependence indicates that the contribution from e-e interactions plays 44 . 9. Heeger.2 K follows a T1/2 dependence (see Equation 2. Even in highly stretched samples the number of misaligned and criss-crossed chains is rather high so that the σ(T) is nearly identical for both parallel and perpendicular directions to the chain axis. 20-22. Hence.3 [18].J. (Reproduced by permission from M. Menon. A. The dotted lines indicate the power law regime. Ahlskog.2). and the interchain transport plays an important role in both cases. further enhancement in chain orientation (σ⎜⎜/σ⊥ >103) is of considerable importance in order to observe the intrinsic anisotropic features in the charge transport properties in conducting polymers. The anisotropy of conductivity increases upon increasing the stretching ratio. 21]. IOP Publishing. 4145) The σ(T) of I-(CH)x samples at various stretching ratios (l/l0) is shown in Figure 2. 1997. Journal of Physics: Condensed Matter. and it shows a strong negative TCR. (b) W versus T for the same data. R.

E. as ρr increases.B. similar to that observed in the case of I-(CH)x. The optical anisotropy is nearly 50. This indicates that the PPV chains are quite well oriented after tensile drawing. Synthetic Metals. W gradually moves towards the critical and insulating regimes. 69. as explained in detail in Section 2. The temperature dependence of resistivity of a sulfuric acid doped PPV (PPV. as obtained from the dichroic ratio measurement at 1520 cm-1. and H. Elsevier Science SA. 1995. Heeger. Park. the inelastic electronphonon scattering (p = 3/2) is the dominant scattering mechanism for both parallel and perpendicular directions to chain axis [20. Park. The W versus T plot of the same data is shown in Figure 2.3 Conductivity (both parallel and perpendicular) versus temperature for iodine-doped polyacetylene samples at various stretching ratios (l/l0) (Reproduced by permission from C. 45 . Free-standing films of PPV (thickness 4-8 μm) were stretch-aligned to 10:1 ratio [12].O. where σ ∝ T3/4. This suggests that both interaction and localisation play dominant roles in σ(T) at low temperatures in metallic (CH)x samples. Y. The metallic samples follow a positive temperature coefficient of W at low temperatures. Menon. R. 32]. For an intermediate temperature range (4-40 K). 79) a dominant role at very low temperatures.2. Akagi.4a [34.W. Yoon. A.J. Shirakawa. This is also consistent with the enhanced negative contribution to magnetoconductance (MC).4b. 1-3.Electrical Properties of Doped Conjugated Polymers Figure 2. This is also consistent with the enhanced positive contribution to MC at temperatures above 4 K. 35]. K.H2SO4) sample (A) as it gradually aged to sample number (L) is shown in Figure 2.

as observed in the case of metallic (CH)x samples. Noguchi. However.2 [34. the localisation-interaction model is valid at low temperatures. at temperatures below 4 K. the T1/2 fit is rather good even in the presence of a magnetic field. Although the anisotropy of conductivity in metallic. 35]. The W versus T plot of the same data is shown in Figure 2. in metallic PPV samples. Moreover. as explained below. 11.5b. Hence. Heeger.Handbook of Polymers in Electronics (a) (b) Figure 2. as shown in earlier works [34]. 55. R.4 (a) Resistivity versus temperature for a PPV-H2SO4 sample from metallic (highly doped) C to insulating (less doped) L and (b) W versus T for the same data.5a [36]. The 46 . (A-E on the metallic side. the low temperature conductivity of metallic samples in both parallel and perpendicular directions to the chain axis can also be fitted to Equation 2. the MC data in both systems are consistent with the localisation-interaction model. American Physical Society.J. oriented (CH)x and PPV samples is nearly 100. Physical Review B. and T. 1997. A. Ahlskog. The temperature dependence of conductivity of PPy doped with PF6 (PPy-PF6) is shown in Figure 2. G-L on the insulating side) (Reproduced by permission from M. Ohnishi. the σ(T) is rather similar in both parallel and perpendicular directions to the chain axis. 6777) In PPV-H2SO4 samples. Menon. T. indicating that an anisotropic three-dimensional model is appropriate in these systems.

American Physical Society. 47 . Heeger. R. The temperature and field dependence of the resistivity of metallic PPy-PF6 samples at temperatures below 1 K shows the presence of a large finite conductivity (∼150 S cm-1) at 75 mK and 8 T field [37]. Hence. and A. 16.Electrical Properties of Doped Conjugated Polymers (a) (b) Figure 2. Menon. Furthermore. Yoon. Physical Review B. the interchain interactions are sufficiently large enough to prevent any severe localisation in polymer chains. PPy-PF6 samples can be stretched by a factor of two. The behaviour of W(T) is consistent with that observed in metallic (CH)x and PPV samples. I→ for insulating. 49. 10851) metallic sample (M1) shows a positive TCR below 12 K.J. D. although the conductivity at mK temperatures in these systems is around the minimum value of conductivity of a metallic substance according to Mott’s theory [24].O. and their conductivity increases up to 3000 S cm-1 [13].5 (a) Normalised resistivity versus temperature for various PPy-PF6 samples (M→ for metallic. 1994. and m′ in Equation 2. This is one of the best examples of conductivity in a doped conjugated polymer that has a long-term stability at ambient conditions. and ‘c’ for critical) and (b) W versus T for the same data (Reproduced by permission from C. This suggests that the three-dimensional transport is quite robust and that the intrinsic one-dimensional nature of disordered polymer chains is not causing any severe localisation. Moses.2 is negative.

Abell. Figure 2. 1998.6 Conductivity versus temperature for PANI-AMPSA samples at various doping levels mentioned in subscripts (Reproduced by permission from P. its positive TCR is observed down to much lower temperatures. IOP Publishing. and A.N. 37-38.J. 8293) 48 .and AMPSA-doped PANI samples is possibly due to the variations in microstructure and its contribution to disorder-induced localisation. Devasagayam. S.Handbook of Polymers in Electronics The σ(T) of 2-acrylamido-2-methyl-1-propane-sulfonic acid (AMPSA) samples are shown in Figure 2. Adams. Although the σ(300 K) of PANI-AMPSA samples is slightly lower with respect to PANICSA. 10. L. Journal of Physics: Condensed Matter. Pomfret. These samples show a positive TCR at temperatures above 80 K. The difference in σ(300 K) and σ(T) between CSA. 39]. P. Monkman. The wet spun PANI-AMPSA fibres have shown an impressive room temperature conductivity of nearly 2000 S cm-1 [40]. This shows that the charge transport in doped conducting polymers is rather sensitive to slight variations in the morphological features.6 [38.P.

One possible explanation is that the structural disorder in PEDOT samples is considerably less with respect to other systems.4-ethylenedioxy-thiophene). and A. Aleshin. R. PEDOT. In these systems. from metallic BF1 to insulating BF5) (Reproduced by permission from A.J. even for samples with σ(300 K) ≈10 S cm-1 (i. much below the Mott minimum value). In summary.e. the chain extension is possible only through the α-positions. 42]. Figure 2. PPV. Kiebooms. it is possible to observe the intrinsic metallic positive TCR in doped conducting polymers. 1997. PANI and PEDOT samples suggests that by reducing the role of disorder-induced localisation in charge transport. Heeger. as shown in Figure 2. Masubuchi and co-workers have observed a pressure tuning of the M-I transition [43. a positive TCR have been observed at temperatures below 10 K. the conductivity and its temperature dependence in doped (CH)x.7 Normalised resistivity versus temperature for various doped PEDOT samples (from metallic PF1 to insulating PF6. Similar positive TCR and weak σ(T) values have been observed in poly(3-methyl)thiophene (PMeT)-PF6 samples having σ(300 K) ≈ 200 S cm-1. 61) 49 . In some doped PEDOT samples. 44]..7 [41.Electrical Properties of Doped Conjugated Polymers The σ(T) of doped poly(3.7. Synthetic Metals. In doped PEDOT samples. Elsevier Science SA . since the β-positions in the thiopene rings are blocked by an ethylenedioxy group. Menon. PPy. samples are shown in Figure 2. 90. 1-3. the conductivity at 1 K can be around 4 S cm-1. the σ(T) can be exceptionally weak. R. For example. A large finite conductivity [~150 S cm-1] has been observed in metallic PEDOT and PMeT systems too.

scattering process.2. the fine features in anisotropic MC can be made inconspicuous in the presence of disorder.Handbook of Polymers in Electronics 2. the MC can be used as a powerful tool to investigate the intrachain versus interchain transport.g. PEDOT) the MC is observed to be negative at all temperatures and fields [31].) in metallic and semiconducting systems [18]. 32]. etc.. which is probably associated with the anisotropic diffusion coefficient.e. the sign of the MC depends on the angle between the magnetic field and chain axis. anisotropic effective mass. Highly conducting. and the hopping contribution to MC (large negative MC) increases. The quantitative level of understanding of MC for disordered systems obtained using the localisation-interaction model is rather useful to check the appropriateness of this model for metallic conducting polymers. The behaviour of MC in oriented and unoriented conducting polymers shows a clear difference. Nevertheless. It is well known that in an ideal one-dimensional conductor the transverse orbital motion is restricted. 34. thus the carriers cannot make circular motion in the presence of a magnetic field. oriented samples (e. Δσ/σ < ± 3%). in unoriented samples (e. the WL contribution (positive MC) dominates at temperatures greater than 4 K and low fields (below 3 T) and the contribution from e-e interaction (negative MC) dominates at temperature below 4 K and higher fields (above 3 T). PPy.g. However. 45]. 35]. as the extent of disorder increases. There are several detailed studies of MC in conducting polymers [18. since the positive MC due to the WL contribution is maximised when the field is perpendicular to the chain axis.. In oriented samples. etc. PANI. in the presence of any finite interchain transfer integral. and it is minimised when the field is parallel to the chain axis [32. Moreover. it is well known that the quantum corrections due to weak localisation (WL) and e-e interactions contribute to the MC at low temperatures [18. whereas. the observed MC in oriented metallic conducting polymers is slightly higher. Usually. 50 . In disordered metallic systems. This anisotropic MC in oriented samples is due to the anisotropy in the WL contribution. when the field is perpendicular to the chain axis) at temperatures greater than 2 K. one could hardly expect any MC in an ideal one-dimensional conductor.g. Although the theoretical estimate for the upper limit to the quantum corrections to MC in conventional disordered systems is below 3% (i. relaxation mechanism. as in several q-1D conductors.. (CH)x and PPV) exhibit a positive MC due to the WL contribution (especially. However.. 32. the consistency of using this model can be verified by comparing the results from the temperature dependence of conductivity and MC measurements. both WL and e-e interaction contributions decrease.2 Magnetoconductance It is well known that MC is a sensitive local probe for investigating the microscopic transport parameters (e. Hence. the MC is an interplay between WL (positive MC at low fields and temperatures greater than 2 K) and e-e interaction (negative MC at high fields and temperature less than 2 K) contributions.

23. Heeger. 15529) The MC for oriented metallic I-(CH)x and PPV-H2SO4 samples are shown in Figure 2. R. 1994. and D. and T.4 K. Ahlskog. Physical Review B. 53. Noguchi.8a [32] and (b) [34. Although the aged sample remains metallic down to 1.2 K (triangle). As shown in these figures. respectively. 16162) (b) Magnetoconductance versus field for a metallic PPV-H2SO4 sample.2 K (dot). the sign of the MC is negative. However. Y. 1996. K. Moses. In both systems. A. The experimental results in both systems show that the WL contribution is negligible when the field is parallel to the chain axis. the positive MC due to the WL contribution vanishes owing to the increasing extent of disorder caused by the aging. the sign of the MC is positive. upper is transverse and lower is longitudinal (Reproduced by permission from M. 35]. Menon. Menon. American Physical Society. upper is transverse and lower is longitudinal (Reproduced by permission from R. 23. the anisotropy of conductivity is nearly 100.Electrical Properties of Doped Conjugated Polymers (a) (b) Figure 2. American Physical Society. Ohnishi. when the field is parallel to the chain axis. 2 K (square) and 1. Cao. Vakiparta. This indicates that even a marginal increase in the extent of disorder in metallic conducting polymers 51 .J.8 (a) Magnetoconductance versus field for a metallic I-(CH)x sample at 4. T. Physical Review B. when the field is perpendicular to the chain axis. 49.

Hence. 15529) 52 .J.9b.9a. American Physical Society. disorder. The scaling plot for a metallic oriented PPV-H2SO4 sample is shown in Figure 2. as shown in Figure 2. Noguchi and T. 23. However. This clearly shows the importance of the WL contribution to the transverse MC. is clearly shown in Figure 2. A. Ohnishi al. Menon.9 Universal scaling plot of magnetoconductance for a metallic PPV-H2SO4 sample: (a) transverse (b) longitudinal (Reproduced by permission from M. in the case of transverse MC. the coherent interchain transport in intrinsically q-1D polymer chains can be easily affected by minute variations in the interchain alignments.. Ahlskog. Heeger. the scaling behaviour deviates. The MC due to the e-e interaction can be distinguished from the WL by scaling the total value [34. etc. 1996. 53. This anisotropic MC can be used to probe the microscopic anisotropy at the molecular length (a) (b) Figure 2. R. 46]. Physical Review B.Handbook of Polymers in Electronics can suppress the quantum transport involved in the WL contribution to a positive MC.9. due to the dominant contribution from e-e interaction. T. The expected universal scaling behaviour in the longitudinal MC.

24 K) (Reproduced by permission from A. R. modelling the anisotropic MC can provide a quantitative estimate of the number of misaligned chains in oriented samples.02 K. indicating that the e-e interaction is the dominant contribution to the MC. The MC shows H2 and H1/2 dependence at low and high fields.10 [41. 56. since the chains are not oriented. The MC for a metallic PANI-CSA sample. Kiebooms. as shown in Figure 2.03 K. is shown in Figure 2. Wudl. and A. closed triangles 4. Heeger.48 K. 3659) scale which is usually masked by the morphological features in the bulk conductivity measurements. This field dependence is consistent with the localisation-interaction model. This suggests that high quality oriented conducting polymers behave as anisotropic three-dimensional systems in which the charge transport mechanism is nearly identical in both parallel and perpendicular directions to the chain axis. at low and high fields. Similar results have been observed for metallic PPy [36] and PEDOT [41] samples.PF6 sample at various temperatures (dots 1. 7. F. the scaling behaviour is nearly identical in both transverse and longitudinal MC. diamonds 2. respectively. American Physical Society. In slightly less conducting (~ 100 S cm-1) metallic samples of unoriented PEDOT a universal scaling of the MC has been observed. Menon. open triangles 3. the behaviour of the MC is identical whether the current is parallel or perpendicular to the chain axis. Although the anisotropy of conductivity in metallic oriented-(CH)x or PPV-H2SO4 samples is nearly 100.11 [15]. R. Hence. These systems are just 53 . 42]. Aleshin. Physical Review B.10 Universal scaling plot of magnetoconductance for a metallic PEDOT. In this case.J.Electrical Properties of Doped Conjugated Polymers Figure 2. 1997.

Heeger. 1993. A. and their values of conductivity are not high enough to observe any positive MC due to the WL contribution. 54 . the MC in metallic conducting polymers is a sensitive probe for investigating the microscopic charge transport mechanism.11 Magnetoconductance versus field for a metallic PANI-CSA sample: (a) low field fit and (b) high field fit (Reproduced by permission from R. and Y. 48. In summary.Handbook of Polymers in Electronics (a) (b) Figure 2. In less conducting and unoriented systems. and this can give qualitative information regarding the molecular scale anisotropy in these systems. 17685) on the metallic side of the M-I boundary. D. Cao. In oriented metallic conducting polymers. in PANI. Menon. the anisotropic MC depends on the angle between the chain axis and the applied field. American Physical Society. When the extent of disorder increases and the system moves to the critical and insulating regimes the negative MC increases dramatically. Physical Review B. the MC remains negative at all temperatures and fields. Hence. 24. C.O. PPy and PEDOT systems.J. the magnitude of the negative MC increases as ρr increases. Moses. Yoon. and this can be used to discover the extent of disorder present in the system.

and n-type doped (CH)x. the thermoelectric power is not as sensitive to disorder as electrical conductivity. Kaiser [47] has proposed a heterogeneous model to explain the apparent difference in the behaviour of S(T) and σ(T). since the mean free path involved in the electrical transport is very much affected by the extent of disorder present in the system [18]. determine the bulk transport properties. In these systems the quasi-linear thermoelectric power is relatively insensitive to the variations in ρr near the disorder-induced M-I transition.12 [36].2. A large enhancement of thermoelectric power is expected if the barriers play any significant role to the total value of the thermoelectric power. etc. The conventional notion suggests that the sign of the thermoelectric power depends on the sign of the charge carrier. However. then the system indeed shows a metallic thermoelectric power. the less conducting regions that limit the motion of charge carriers. The S(T) of various PPy-PF6 samples on both sides of the M-I transition is shown in Figure 2. is quite usual in all conducting polymers for a wide range of temperatures (10-300 K). The density of states estimated from S(T) is around one state per eV per two rings for PANI-CSA. The quasi-linear temperature dependence of thermoelectric power is observed to persist well into the insulating regime. for samples near the M-I transition.3 Thermoelectric Power In doped conducting polymers.Electrical Properties of Doped Conjugated Polymers 2. The S(T) is quite linear even in the case of samples on the insulating side of the M-I transition [18]. Although the metallic positive TCR is rather unusual in highly conducting polymers for a wide range of temperatures. and nearly one state per eV per four rings for PPy-PF6. this indicates that the barriers contribute little to the thermoelectric power. 55 . S(T). More work is required to fully understand this anomaly regarding the sign of thermoelectric power in conducting polymers. Park and co-workers [49] have observed a positive thermoelectric power for both p. the metallic linear temperature dependence of thermoelectric power. If the thermal current carried by phonons is impeded less by thin insulating barriers than the electrical current carried by electrons or holes. no such enhancement has been observed. Since the sign of the thermoelectric power depends on the band structure. Similar results have been observed in PANI-CSA samples too [48].. The remarkable linearity of S(T) and the negligible non linear contribution to thermoelectric power in high quality metallic (CH)x indicate that the lattice contribution to thermoelectric power due to phonons is less significant. In other words. the majority of the temperature gradient occurs across the highly conducting regions and the majority of the electrical potential drop occurs across the thin insulating barriers. it may not be that straightforward in complex systems such as doped conducting polymers. in conducting polymers. on the metallic and critical regimes of the MI transition. However. In such a model.

4 Magnetic Susceptibility and Specific Heat In metallic systems.Handbook of Polymers in Electronics Figure 2.2.O. Yoon. Heeger. respectively [51]. i. A small Curie term has been observed in all metallic conducting polymers at very low temperatures (T < 20 K) [18]. Usually. The Pauli susceptibility is directly proportional to the density of states at the Fermi level. Menon. The density of states at the Fermi level for metallic PANI-CSA and PPyPF6 samples are one states per eV per two rings and three states per eV per four rings. The χ(T) of PANI-CSA samples near the M-I transition show this behaviour [50]. This indicates the presence of localised spins due to impurities. 56 . The Curie term at low temperatures is lower for metallic samples than for insulating samples. it is possible to determine the N(EF) from the temperature-independent χP for metallic systems. 49. These values are rather similar to that obtained from the thermoelectric power measurements. 16. R. the temperature-independent Pauli susceptibility (χP) is a characteristic feature for delocalised carriers [18]. defects. the measured χP is the sum of both Curie and Pauli terms. The magnetic properties and spin dynamics in doped conducting polymers are described in recent review articles [51]. Hence. in disordered systems. D. Physical Review B. American Physical Society. and A. the Curie term gives an estimate of the localised spins present in the system. 1994.J. and this in turn is a measure of the extent of disorder. etc.12 Thermoelectric power versus temperature for various PPy-PF6 samples from metallic side (dot) to insulating side (square) (Reproduced by permission from C. Moses. 10851) 2.e. where μB is the Bohr magneton and N(EF) is the density of states at the Fermi level. χP = μ2BN(EF).

66. The comparison of specific heat and conductivity data 57 . etc. The linear term in specific heat at low temperatures is evidence of the continuous density of states with a well-defined Fermi energy for any metallic system.13 Heat capacity (C/T) versus temperature for doped PPy samples from metallic PPy-PF6 (circles) to insulating PPy(TSO) [triangles] (Reproduced by permission from T.6±0. the calculated density of states for metallic and insulating samples are 3.04 states per eV per unit.12 and 1. 53]..e. for a metallic PPy-PF6 sample and for an insulating PPy-p-toluenesulfonate (TSO) sample is shown in Figure 2.2±0. and the density of states of the insulating system is only a factor of three lower with respect to that in the metallic sample [51]. thermal conductivity. both systems show a linear term in specific heat.3 K. C. Moreover. The low temperature specific heat. These values are comparable to those obtained from the spin susceptibility data. From the values of β and γ.13 [54]. hence the insulating system can be considered as slightly less metallic (less density of states due to localisation) with respect to the ‘real’ metallic system (i. 3. from the specific heat data [54] it seems that both systems have a finite density of states at the Fermi level. Ishiguro. Although the resistivity ratio of the insulating PPy-TSO sample is an order of magnitude larger with respect to the metallic PPy-PF6 sample. where γ and β are the electronic and lattice contributions. Journal of the Physical Society of Japan. specific heat.) [52. and the corresponding Debye temperatures are 210±7 and 191±6. The data for both samples fit to the equation C/T = γ + βT2. respectively. Physical Society of Japan.g. finite conductivity as the temperature tends to 0 K). respectively. 727) There are few reports of thermal property measurements (e. Gilani and T.. 1997.Electrical Properties of Doped Conjugated Polymers Figure 2.H.

one-dimensional localisation. the effect of disorder is not that conspicuous near the M-I transition. both systems do not show any anomalies due to glassy behaviour that can occur due to the localisation of charge carriers in the amorphous regions. In all these figures. as shown in case of a PPy-PF6 sample in 58 . contrary to the conventional view that all states are localised in a disordered one-dimensional conductor. However. This indicates that for conducting polymer samples near the M-I transition.14 [55]. 2.. the system gradually moves from the metallic to the insulating state via the M-I transition. Usually. the critical regime can be easily tuned to the metallic and insulating regimes by pressure and magnetic fields. where γ = 1/(d +1) and d is the dimensionality of the system. The value of β and the temperature range of the power law regime can be determined from the log-log plots of W versus T. Surprisingly.. especially in conducting polymer systems. σ(T) ∝ exp(-T 0/T) γ.e. and for discerning the metallic and insulating systems near the M-I transition. The power law behaviour of conductivity is universal for systems at the critical regime. 2. As the extent of disorder increases. specific heat.4b and 2. although a Curie term in the spin susceptibility was observed for all conducting polymer samples at low temperatures. in other transport property measurements like thermoelectric power. where β is between 0. In the power law regime (temperature-independent W(T) regime) W(T) = β. Furthermore. 20]. From the previous section it is known that even slight variations in the extent of disorder have dramatic effects in the temperature dependence of conductivity near the M-I transition.Handbook of Polymers in Electronics indicates that the latter is more sensitive for determining the extent of disorder.33 and 1 [20]. the W versus T plot of various conducting polymer systems near the critical regime is shown in Figure 2. and as ρr increases the system moves towards the insulating regime in which σ(T) becomes exponential. the effective conjugation length and the interchain transport decreases.5b.3 Critical and Insulating States The intrinsic metallic state in high quality doped conducting polymers is suppressed by disorder-induced localisation [18. etc. critical (temperature-independent) and insulating (negative) regimes. Moreover. The W versus T plots for various conducting polymers are shown in Figures 2. respectively. and the temperature dependence of conductivity is given by σ(T) ∝ Tβ. As a typical example.2b. the value of β is lower for systems with a smaller value of ρr. the extent of disorder is not severe enough to induce any drastic localisation of charge carriers. These figures clearly show that the critical regime is rather robust in conducting polymers. i. etc. the temperature coefficient of W(T) varies distinctly for metallic (positive). the linear term in the specific heat is strongly present in both metallic and insulating systems down to 2 K.

329) Figure 2. Y. Yoon. oriented I-(CH) x (open square). from metallic to critical regime. and slight variations in the overlap of the wavefunctions of the delocalised states by magnetic field. PPy-PF6 (dark triangle) and PANI-CSA (dark circle) (Reproduced by permission from R. 16]. 69. etc.16 [35]. Synthetic Metals. disorder. and the field shrinks the overlap of the wavefunctions of the delocalised states. oriented K-(CH) x (dark square). Menon.15 [55]. Cao and A. These field-induced transitions in conducting polymer systems near the M-I transition show that the mobility edge and the Fermi level are situated rather close to each other. Although this sample has a large finite conductivity in zero field. The enhanced interchain transport under pressure is driving the system towards the metallic state. 1-3. it approaches zero at 8 T. from power law to exponential law behaviour of conductivity at low temperatures. Another typical example of a field-induced transition.. Heeger. The negative magnetoresistance (MR) in metallic (CH)x and PPV samples is quite sensitive to the extent of disorder [18.Electrical Properties of Doped Conjugated Polymers Figure 2.O. 1995.17 [15. Moses. is shown for a PANI-CSA sample in Figure 2. Elsevier Science SA. for a doped PPV sample is shown in Figure 2. Alternatively. 20]. the field-induced transition to the critical and insulating regimes occurs when the localisation length is comparable to the magnetic length. could alter the electronic properties of the system. Even in the case of oriented metallic samples of (CH)x 59 . D.14 W versus temperature plot for various conducting polymers in the critical regime of M-I transition: unoriented I-(CH) x (open circle).J. C. The field-induced transition.

D. 1-3. Y. Elsevier Science SA. C. and T. Noguchi. Menon. 1995.4) at 0. Yoon. Ahlskog. Physical Review B.16 Field-induced transition from metallic to critical regime: (a) W versus temperature for a metallic PPV-H2SO4 sample (E from Figure 2. Heeger. A. Synthetic Metals. 6777) 60 .1 for same data (Reproduced by permission from M. Heeger. Cao and A. 11. 55.J.O. 69. 5 and 8 T fields and (b) conductivity versus T0. R. 1997. Moses. Menon.J. Ohnishi.15 W versus temperature plot for a PPy-PF6 sample in the critical regime: pressureinduced transition to the metallic side and the field-induced transition to the insulating side (Reproduced by permission from R. American Physical Society. 329) Figure 2. T.Handbook of Polymers in Electronics Figure 2.

PEDOT.18 [36]. Moses. as ρr increases the positive MR increases. 45].Electrical Properties of Doped Conjugated Polymers Figure 2. 1993. critical and insulating regimes are less than 5%. The MR is positive at all temperatures and fields in PANI. As disorder increases and the system moves towards the critical and insulating regimes. Physical Review B. 48. The typical values of the magnitude of positive MR at 1. Cao. in the metallic.J.4 K and 8 T field. Heeger. and the hopping transport becomes more difficult at higher fields and 61 . the contribution to positive MR increases. Yoon. since the chains are less oriented in these systems with respect to (CH)x and PPV [20]. a marginal increase in disorder can easily suppress the quantum interference process involved in the WL contribution to negative MR [35.. PMET.O. as shown in the case of PPy-PF6 samples in Figure 2. the positive MR contribution increases due to the shrinkage of the overlap of the wave function of the localised states. 24.17 Field-induced transition from critical to insulating regime for PANI-CSA samples: resistivity versus T–1/4 plot. C.26 and H = 0 T (dark square) and H = 8 T (dark triangle) for a sample with ρ(T) ∝ T–0. and Y. American Physical Society. In these systems. The large positive MR in the VRH regime is due to the shrinkage of the overlap of the tails of the wavefunctions of the localised states. In conducting polymers. between 5% and 20%. as the chain orientation decreases. the magnitude of the positive MR can be used to obtain a rough estimate of the extent of disorder present in the system. D. H = 0 T (dark dot) and H = 10 T (dark diamond) for a sample with ρ(T) ∝ T–0. and larger than 20%. Hence. A. etc. Menon. PPy. Usually the magnitude of the positive MR at very low temperatures (T < 4 K) is as sensitive as the temperature dependence of conductivity for probing the extent of disorder present in the sample. 17685) and PPV. respectively [18].36 (Reproduced by permission from R.

etc. Usually the negative hopping contribution can be estimated by subtracting the diffusion contribution. the MR data is complementary to the low temperature conductivity data in probing the extent of disorder present in critical and insulating systems.Handbook of Polymers in Electronics Figure 2. Menon. Heeger. Yoon. 10851) lower temperatures. In the VRH regime. as the system moves to the highly disordered granular. Moses. 56]. A typical example of this feature is shown in Figure 2. and this can be used to determine the localisation length in the insulating regime. If the localisation length is of the order of few hundreds (few tens) of Angstrom then the extend of disorder is relatively low (high) [56]. 49. The gradual variation of S(T) from the positive linear temperature dependence to the negative temperature dependence can be correlated with the microstructure.O. and A. These features in S(T) can be used to obtain a qualitative picture about the macroscopic scale disorder present in conducting polymers.. 1994. specific heat. The linear temperature dependence of thermoelectric power and a linear term in the specific heat (which are typical for metallic systems) have been observed in the insulating regime too. 16. are important in the critical and insulating regimes.19 [20.18 Magnetoresistance versus resistivity ratio (ρr) for various PPy-PF6 samples from metallic to insulating side (Reproduced by permission from C. metallic islands. R. like thermoelectric power. As the system moves into the insulating side the hopping contribution to thermoelectric power (Shop ∝ T1/2) dominates over the metallic diffusion thermoelectric power (Sdif ∝ T) [56]. 62 . Hence. the low field MR follows a H2 dependence.J. Physical Review B. Although transport property measurements. American Physical Society. they are not as sensitive as the low temperature conductivity and MR. and this gives an estimate of the extent of disorder present in the macroscopic level. D.

χ(T) is not as sensitive as σ(T) and MR for identifying the metallic. etc. Menon. 229) The Curie term in χ(T) is rather dominant at low temperatures for systems in the critical and insulating regimes. Y. Elsevier Science SA. Reike. are strongly governed by both microscopic and macroscopic level structural disorder. 63 . R.19 Hopping contribution to thermoelectric power for various doped PANI samples (Reproduced by permission from C. However.O. Yoon. 1995. Cao. in which the structural and morphological features influence the electrical and optical properties significantly. Heeger. 75.J. and the temperature independent Pauli term is usually observed at temperatures greater than 100 K.. D. The charge transport properties. 2. Moses. D. X. T. 1-3. Synthetic Metals. doping-induced disorder.Electrical Properties of Doped Conjugated Polymers Figure 2. critical and insulating regimes near the M-I transition [17]. A. etc.4 Summary This brief overview of the electrical transport properties in doped conducting polymers highlights the following points: (1) Conducting polymers are rather complex systems. the M-I transition. Wu and R. Chen.A.

the anisotropic MC due to the interplay of WL and e-e interaction contributions (i. the doping level. PPV. linear term in specific heat. at low temperatures. metallic reflectance and free carrier absorption in the infrared. the electronic states are delocalised along the chain direction. linear temperature dependence of thermoelectric power. This suggests that the charge transport mechanism is nearly identical in both parallel and perpendicular directions to chain axis. In oriented materials. both localised and delocalised states coexist as an interpenetrating network. etc. charge transport mechanism.. The universal scaling behaviour of the MC confirms the dominant role of the e-e interaction contribution. (5) A metallic state has been observed in high quality samples of doped (CH)x. polarons. PMeT and PEDOT. temperature independent Pauli susceptibility.. disorder-induced localisation. the sign of MC is positive (negative) when the field is perpendicular (parallel) to the chain axis) can be used to probe the misaligned chains. and the system behaves more like an anisotropic 3D system. (3) In doped conducting polymers. (7) The √T dependence of conductivity. as a result the conductivity. in metallic conducting polymers indicates that the e-e interaction contribution is significant. interchain interaction. PANI. the effective conjugation length. These features show the intrinsic metallic nature of doped conducting polymers. etc. are higher with respect to unoriented systems. etc. quantum corrections (weak localisation and e-e interaction) to MC. in doped conducting polymers.5 K in ClO4-doped (CH)x. In several metallic conducting polymer samples a positive TCR has been observed at temperature below 20 K. bipolarons. In PANI-AMPSA (CSA) the positive TCR is observed at temperatures greater than 70 (150) K. The experimental evidence indicates the following: finite conductivity at mK temperatures. etc. PPy. determine the stability of solitons. 64 . free carriers.e. (9) The behaviour of σ(T) and MC is nearly identical in both parallel and perpendicular directions to the chain axis in highly oriented metallic (CH)x and PPV. (8) In oriented metallic systems. (4) The molecular structure. the localised states determine the charge transport properties. interchain interactions and morphology are the important parameters that influence the physical properties. (6) The metallic positive TCR has been observed from 300 to 1.Handbook of Polymers in Electronics (2) In general. the extent of disorder. In unoriented globular or granular conducting polymer systems. the carrier mobility...

Ed. Kaneto. 4. Schrieffer and W. Volumes 1-4. New York. Kivelson. Elsenbaumer and J. 69.. New York. Chemical Communications.. Handbook of Conducting Polymers. J. from metallic to critical and from critical to insulating regimes. Heeger. 1986. the resistivity ratio and positive MR increases as the extent of disorder increases. Dordrecht. C.K. USA. Boston. A. Su. Shirakawa.G. Singapore. conducting polymers are at the M-I boundary. MacDiarmid.J. Skotheim. K. temperature-independent and negative temperature coefficients of W(T) corresponds to metallic. 1994. respectively. Heeger. E.L.R. Conjugated Conducting Polymers. Eds. References 1. Volume 102. 781. 65 2. Handbook of Organic Conductive Molecules and Polymers. H. 1988. Ed. (11) In the critical and insulating regimes. 1992. Yoshino and Y.A.J. critical and insulating regimes can be identified from the W versus T plots. 6. 578 (1977). Chiang and A. Netherlands. A. Volumes 1 and 2. show that the mobility edge and Fermi level are situated rather close together. Spaepan.R. NY. due to interchain transport and disorder. Reynolds.S. T. Hence. 60. Germany. Academic. For a review see A. 1985. H. Solid State Properties of Fullerene. Graja. Ed. USA. New York. Eds. World Scientific. a semiquantitative level of information about the extent of disorder can be obtained. Marcel Dekker. critical and insulating regimes. Ehrenriech and F. Reviews in Modern Physics. 3-4.J. 2nd Edition. Ed. NY. P. T. (12) From the hopping contribution to the S(T) and the Curie term in χ(T). Nalwa. 1992.. Handbook of Conducting Polymers. 5. The field-induced transitions. 8.P. Inushi in Electronic Properties of Inorganic QuasiOne-Dimensional Materials. Springer Series in Solid State Sciences. 3. Volume II. Louis. 9. H. .. S.Electrical Properties of Doped Conjugated Polymers (10) The metallic. Skotheim. Journal of the Chemical Society.. Marcel Dekker. Kiess. Monceau. H.A. USA.. R. 1998. Springer. Berlin. Wiley. Low-Dimensional Organic Conductors. K. The positive.G. USA. 1997. MA. NY. 7.

R.O. Murase. 1997. Elsenbaumer and J. 1987. M. 1993. 509. Moses and A. 1995. 1958. Nakano. K. Sariciftci. Lee and T. Physical Review B. 385. Metal-Insulator Transition. R. Hirooka and I. USA. 1992. Heeger and Y. Menon.. 27. Heeger in Handbook of Conducting Polymers. 22. C. 1-2. Synthetic Metals. T. S. 904.J. McCullough and R. Hagiwara. 21. Synthetic Metals. New York. 7171.J. Physical Review B. Tsukamoto. T.L. 1993. 7.S. Physical Review. T. T. Journal of Physics: Condensed Matter. World Scientific.S. S. Roth and H. 1998. Ohnishi. 1991. Yoon. 20. 15. Ramakrishnan.V. Moses and A. N. Ed. D. Eds. Yoon. M. 19.. 17. 18.J. 26. Nalwa. 5. 47. 31-33. P. Cao. 1990. New York. 1990. 17685. USA. London. Noguchi. 1998.F. Reviews of Modern Physics. Y. Choi and D. H.W. 109. Heeger. 1992.J. 1985. 1993. Singapore. 24. 91.W. Cao. Synthetic Metals. 309. 4137. Park. 1492. 36. Y. R. 4. Advanced Physics. Taylor & Francis. 241. M. NY. 1-3. Synthetic Metals. Menon. Menon in Handbook of Organic Conductive Molecules and Polymers. 1758. Ed. R. 2nd Edition. 96. R. Hirasaka. 11. Yamaura. Lowe. 1998. 1997. NY. 41. 48.D. Menon. 70. Menon.S.A. 23. Physical Review B. 3-4. Mott.. 13. R.A. T. Sato and M. Bleier. D. Reynolds. 51. D. Skotheim. 287. Suh. 25. Y. 12. Anderson. UK. Marcel Dekker. P. 36. 1-2. N. 24. 16. Ahlskog and R. Moses. 81. A. 66 . Wiley. 41-43.S. E. Heeger.D. Primary Photoexcitations in Conjugated Polymers. Cao. 10. 48. 32. Journal of Organic Chemistry. J. 47. Advanced Physics. 14. 57.Handbook of Polymers in Electronics 10. 4-6. Smith and A. 5-8. Stafstrom.O. C. 1-3. P. 2nd Edition. Volume 4. 1-3.R.

Ohnishi. D. Ihas. 215. E. Adams. M. 37-38. 1-4. 15529.J. 1-3. Holland.J.J. 23. Physical Review B. Heeger. Menon.] 30.J.G. 1. 1994. Menon.N.J. Noguchi and T. Kiebooms. P. 1997. 727. 37. 56. Vakiparta. Heeger. 1992.J. 10.J. P. R. Journal of Physics: Condensed Matter.P. 3659. 49. Physical Review B. 40. Pomfret.P. 1984. 90. 39. 1989. 55. 1-3. 34. T. C. P. Ishiguro.N. Advanced Materials. 35. Heeger. 59. A. 9. Kiebooms. 8293. 1351. Dai. 65. 10851. 2991. 1997. Menon and A. 36.P. 371. Pietronero. Devasagayam. Monkman.J.W. N. 32. 41. Zhang and M.J. 1984. 31. F. 6777. 425. 7. H. A. Monkman. 141. 4145. 1997. G. M. Moses. S. C. Heeger. Ahlskog. T. 1998. 23. L. 11. 11. L. 1997.J. Cao and D. 61. Kaneko and T. 33.N. Synthetic Metals.R. R.O. Pomfret. Journal of Physics: Condensed Matter. P. Heeger. 46. R. Heeger. Ohnishi. 16162. Physical Review B. M. Menon. Aleshin. J. 1-3. 16. R. 1994. Meisel. A. 69. Phys. R. A. A.P.O. Synthetic Metals. Ahlskog.J. 22. 67 . 1998. Heeger. Ahlskog. A. 10. 86. 29. Synthetic Metals. K. 53. 16. 15-17. Menon. [Sov. Sarachik. 42.G. Rafanello. S. Physical Review B. 6724. Journal of Physics: Condensed Matter. Cao and A. Menon and A. R. Zeninova.Electrical Properties of Doped Conjugated Polymers 27. Menon.C. 8. 1983. Comfort and A. Zhurnal Technicheskoi Fiziki. R. Synthetic Metals. Adams. Clark. Monkman. Menon. Yoon. 1995. Pomfret. 225. 1996. M. Heeger. P. R. Wudl and A. R. 1994.P.J. 28. Y.N. 38. 8. Abell and A. Physical Review B. Moses and A. JETP. Aleshin. Y. 20-22. R. S. Y. 49. Kievelson and A. Adams and A. S. Noguchi and T. Physical Review B. Yoon. Synthetic Metals. Zabrodskii and K. 1996.

Mizoguchi and S. Akagi and H. Physical Review B. 9.G. 50. 54. Park. 1995. Piraux. and J. 69. 1-3. 43.B. Fukuhara and S. 1994. C.S. Yoon. 84.P. 601.S. 1-2. Heeger. Synthetic Metals.Y. Shirakawa. Chen. 329. Kazama. 727. Kazama. 61. Pron. Takahashi.. N.D. Physical Review B. R. D. J. 74. Tsukamoto. Synthetic Metals. 2806. Yoon. Physical Review B. 11829. 1-3. Moses. Volume 3.O. 66. Begin and D. 75. Synthetic Metals. D.J. Kaiser. 129. 53. Cao. Dai. Masubuchi. Cao. USA. P. Bogdanovich. 47.J. 52. 1995. Journal of the Physics Society of Japan. Heeger and Y. Moses. Wiley. 92. T.J. D. L. E. Physical Review Letters.Handbook of Polymers in Electronics 43. H. 1995. Moses. Synthetic Metals. Wu and R. K. 55. Physical Review B. Y. New York. Cao. Heeger and A. E. T. Y. S. D. R.. 14080. T. Yoon. T. H. Ducarme. Solid State Commun. A. C. Gilani and T. Reike. 13-14. 68 . 14.H. 56. S. Menon. Menon. Y. H. Park. 1-3. Dobrosavljevic. Kuroda in Handbook of Organic Conductive Molecules and Polymers. K. T. 229.A. Synthetic Metals. Nalwa. 219. J. 1997. MacDiarmid. 5. C. Cao and A. Denenstein. D.O.B. 45. A. Sarachik and V.S. 48. Yoo. 1980. 1995. Ito. 1-3.P. Fukuhara. 49. Y. 229. 2543. A. Heeger and Y. Ed. 1991. 36. 44. 46. 48. 1997.J. Y.J. Sariciftci. 5988. S. A. Masubuchi and S. A. Menon. N. Moses. Kaneko. Synthetic Metals. A. A. Issi. 1991. 1989. 41-43. 1997. Park. 40.O. Ishiguro. A. Heeger. Toyota. 51. 1-3. 19. X. Sasaki. Billaud. 1998. M. 49. R. 69.W. Ishiguro. 1993. Nogami. 3.

The potential of the combination of a signal processing function (active function) using NLO polymers with a signal transmission function (passive function) of transparent 69 . Kaino 3. Among the many types of NLO materials. optical devices should be gathered together in an integrated substrate with optical waveguide structure to control optical signals with low input power. such as glass or polymer waveguides. In these optical systems. The other advantage of using polymers is that they are low in cost and it is possible to fabricate monolithically integrated optical circuits where all the optical devices are combined in one step. To process such information. but also for short distance mutual communication applications. high-speed optical switching devices and parallel signal processing devices are required.1 Introduction The upcoming information technology (IT) era of the 21st century requires processing of large amounts of information accurately at fast speed. since these can be used to process optical signals with a high data transmission rate. Signal processing by optical technology will be a key for that requirement because high-quality and high-speed digital signals can be processed effectively using optical systems. satellite. and cable network. like local area networks. NLO polymers are the most attractive because they may be used to fabricate optical waveguides by standard photoprocesses and it is possible to enhance optical non linearities by synthesising a variety of NLO chromophores (dyes) and attaching them to a polymer backbone. moveable terminal unit. individual subscribers will receive information transmitted via optical fibre cable. NLO polymer devices can be fabricated on planar passive waveguides. optical interconnection and optical device installation in an integrated substrate is important to overcome bottlenecks.3 Non Linear Optical Properties of Polymers for Electronics T. there is a growing interest in the transmission and processing of digital information using non linear optical (NLO) devices. NLO polymer waveguides offer the potential to create highly complex integrated optical devices and optical interconnections on a planar polymer substrate because their optical properties can be tailored by using different types of passive materials and NLO active materials [1]. Within a couple of years. For practical optical signal processing applications. Optical technologies are not only for long haul signal transmission and processing applications. So.

and a highly NLO dye-functionalised polymer usually becomes difficult to process. reactive ion etching (RIE) is an excellent example of waveguide fabrication technology that can be compared to the solvent etching process. the optical transmission length and their processibility [3].e. Processibility of the NLO polymer will also be influenced by the concentration of the dye.2 NLO Polymer Issues for Device Applications The chemical and physical properties of polymers. the development of NLO polymers with thin film or channel waveguide structures directed toward practical optical devices will be discussed. For example. optical loss will increase due to π-π* transitional absorption of the dyes. After patterning. To fabricate polymer channel waveguides with optical non linearity.Handbook of Polymers in Electronics polymers is the most appealing prospect for waveguides made from polymers. Since a high concentration of NLO dyes in a polymer backbone are needed to achieve a large NLO function. 3. the type of optically active materials (i. chromophores or dyes) and the polymer device fabrication processes used decide the applicability. there exists a trade-off between their optical non linearity. This device is based on a combination of an active reconfiguration function with a passive transmission function. including a mask fabrication process. and (2) an NLO ridge waveguide surrounded by a lower refractive index cladding polymer.. a silicon wafer area network using polymer-integrated optics has already been described [2]. the photolithography technique is a basic method to define device patterns in the polymer. direct patterning of the waveguides by using electron beam or laser beam has already been investigated [4]. The inherent chemical and physical properties of the matrix polymer decide the fabrication process. If NLO polymers are used as waveguide device materials. All optical signal processing polymers and electro-optical polymers are presented. Hybrid polymer optical devices for future applications will also be presented. Waveguides with buried structure created via these techniques comprise of two types of compositions: (1) an etched groove backfilled with a NLO polymer. To solve the problem. The embossing process is also used to fabricate polymer waveguides through an inexpensive moulding technique [5]. Hence. Spin coating or casting techniques on substrates such as silicon. because many steps are required. glass and transparent polymer are typically used to create polymer thin films for waveguides. The problem of trying to reduce the waveguide fabrication cost is a highly complicated process. In this chapter. the reduction of transmission loss of the dye-functionalised polymer must be balanced against the enhancement of optical non linearity. 70 . advantages and limitations for creating practical optical devices using NLO polymers.

Practical optical switching devices with nanosecond to picosecond response times have not been developed so far. 3. Transparency in the near-IR region rather than in the visible region is sometimes important because wavelengths of 1. Various kinds of π-electron conjugated polymers have been energetically studied to achieve higher third-order NLO efficiency because many π-conjugated structures are possible and hence absorption wavelengths can be controlled to achieve high efficiency via resonant effect.3 Properties of Third-Order NLO Polymers 3. As will be discussed in Section 3. Thus the reduction of the loss in the near-IR is a critical issue for the telecommunication applications of the NLO polymer waveguide devices. For pico.3 and 1. The stability of the NLO polymer waveguides in high-temperature conditions is also a main issue for practical applications.4.55 μm are used in optical telecommunication systems.to subpicosecond all-optical signal processing systems. and compatibility with other optical systems are also important factors for the development of a NLO polymer waveguide device. polymers are expected to overcome the disadvantages of molecular crystals in mechanical properties and processibility. The deuteration and fluorination of the hydrogen in the polymer is very effective for reducing the vibrational higher harmonic absorption loss of the polymer in the visible to near-IR region [8]. This is because NLO chromophores usually have π-π* transition absorption at visible wavelength which influences the near-IR absorption of the waveguides. Delocalised π-electron conjugated polymers are of great interest because of their potentially fast response time: faster than tens of femtoseconds. In view of practical use. but also the vibrational higher harmonics of the polymer IR absorption [6]. reproducibility. the development of highly efficient thirdorder NLO materials with processibility is required. Reliability. In particular. When discussing the transparency of a polymer. Almost all the passive polymer optical waveguides developed so far have an optical loss of higher than 0. though they suffer from high optical loss in the near-IR region. acceptable cost performance. the alignment of the dye in the polymer matrix which induces the second-order optical non linearity will be lost in high-temperature conditions.1 Background of Third-Order NLO Polymer Research Liquid crystal devices and thermo-optical polymer devices are already being used as switching components with a millisecond response time. not only the absorption of dyes should be considered.5 dB/cm in this region (except for deuterated and/or fluorinated polymer waveguides) [7]. thin films with large optical non linearities 71 .3.Non Linear Optical Properties of Polymers for Electronics High transparency with excellent processibility is needed for NLO dye-functionalised polymers for waveguide applications. Highly efficient third-order NLO polymers can be applied to many optical devices such as thin film and fibre waveguides.

shows a large χ(3) of around 10-9 esu [10].2 Poly(arylenevinylene). NLO properties are also an interesting feature of the PAVs because their precursor polymers are soluble in organic solvents or water. For example. poly [bis(p-toluenesulfonate) of 2. PAVs exist with variations in chemical structure: PPV. Although large χ(3) values have been observed in the crystalline states or uniaxially oriented films of these polymers. which have been reported to show third-order NLO susceptibilities. Among the most studied films are polyacetylene and polydiacetylene (PDA). Polymerisation of a sulfonium monomer. several amorphous or low crystallinity conjugated polymeric NLO materials are presented in the following sections. The length dependence of χ(3) for polyenes and polyynes has already been discussed and it has been revealed that the hyperpolarisabilities increase rapidly with chain length up to 10 repeating units and approach an asymptotic value after about 15 repeating units [9]. PAV PAV electrically conductive. 2. the luminescent wavelength can be dramatically controlled from green to red [15]. of the order of 10-10 to 10-9 esu [9. χ(3). High crystallinity and low processibility prevent its use in optical waveguide devices.5-dimethoxy-p-phenylene vinylene) (MOPPV) [13. These polymers are usually difficult to process because they are rarely fusible and are insoluble in almost all solvents. 3. PTV and poly (2. Good optical quality thin films of PAV have been prepared through a new precursor polymer that is soluble in organic solvents [16]. For example. the high crystallinity or uniaxial domain results in large light scattering losses. good optical quality. By considering this previous research.5-thienylene bis(methylene-dimethyl-sulfonium chloride). by changing their chemical structure. PTV thin film can be fabricated as follows. it has problems in processibility and stability. one of the representative πelectron conjugated polymers. processibility for fabricating thin films by spin coating can be achieved without any modifications of the conjugated length.3. thin films with good transparency are easily obtained from the precursor polymers. Spangler and co-workers have also reported several main chain χ(3) polymers with vinyl structures containing πelectron conjugations in their backbones [12]. These include optical switching and optical signal processing that show applied optical field intensity dependent refractive indices. Jenekhe and co-workers have reported several novel main chain χ(3) polymers with aromatic Schiffs base structure [11]. Hence. PAVs are of special interest as electroluminescent polymers because. other types of amorphous π-conjugated polymers with large χ(3) and good processibility are needed.4-hexadiyne-1. 10]. However. Therefore. 14]. tough.6-diol] (PTSPDA). is carried out in a methanol-water mixture 72 . The non linear electronic polarisation of π-electron conjugated polymers originates from mesomeric effects that depend on the size of the π-conjugated systems.Handbook of Polymers in Electronics have many useful applications in integrated optics.

but the χ(3) peak always appears at the same wavelength. The thermal conversion process of PAV precursor polymers to fully π-conjugated final structure is shown in Figure 3. and even the highly bent non π-conjugated parts between the rigid π-conjugated sequences are converted. As the conversion proceeds from A to F. Controlling temperature and heating time can vary the π-conjugation lengths in PAV. The wavelengths of the χ(3) peaks are 30 nm longer than the absorption peak wavelength of the fully converted film. The χ(3) peak and the absorption peak match each other only when the fully converted state is obtained. The film is heated at 200-250 °C in a vacuum of 10-2 Torr for 5 hours. The steep enhancement of χ(3) from D to F associated with the development of π-conjugated sequences is notable. The conversion proceeds from a non π-conjugated precursor polymer to a fully converted polymer via partially converted copolymers.1.1 Thermal conversion process of PAV precursor polymers to fully π-conjugated final structure 73 . The position of the absorption peak is decided by the maximum sequence present. Conversely. The resulting PTV thin film is chemically stable in air below 10 °C. The reaction is quenched by the addition of hydrochloric acid. At the higher partial conversion level. At the final conversion level. an increase in absorption intensities and red shift of the absorption maxima is observed. short linear sequences are formed. the development of the long rigid π-conjugated sequences is completed. A precursor polymer thin film is obtained by spin coating of the dichloromethane solution of the precursor polymer onto a substrate under inert atmosphere to prevent oxidation with air. These copolymers have both π-conjugated and non π-conjugated sequences for various conversion levels.Non Linear Optical Properties of Polymers for Electronics at –2 °C by adding a methanol solution of tetramethylammonium hydroxide. to give a tough. At the initial conversion level. A yellow precipitate (precursor polymer) appears as the solution is warmed to room temperature. the short sequences have developed into long rigid sequences. the χ(3) peaks are fixed over all conversion levels. flexible PTV film.2 [17]. The conversion dependence of the MOPPV χ(3) spectra superimposed onto that of the absorption spectra is shown in Figure 3. Figure 3. The χ(3) increases due to the three-photon resonant effect at the final conversion level where the long rigid π-conjugated sequences are formed.6 x 10-10 esu. The magnitude of the χ(3) values of the fully converted MOPPV film (F) reaches 1. where A is an arylene unit and X is a halogen.

MOPPV and PPV films . This was caused by three-photon resonant enhancement effects due to the overlap of the third harmonic wavelength with a polymer absorption band. due to their ease in processing films as well as possible good optical quality. copyright 1991.2 x 10 -11 esu. MOPPV and PTV in the absorption wavelength region. n = 4. 1. 3. The χ(3) values of these PAV films evaluated by thirdharmonic generation (THG) measurement at 1.3) thin film [18].475 μm. Elsevier Science Publishers) The optical absorption maxima are revealed to be at 520.8 x 10-12 esu for PTV. The χ(3) values are almost the same for PPV.85 μm are found to be 5.2 Conversion dependence of the MOPPV χ (3) spectra superimposed on their absorption spectra (Reproduced with permission from [17]. is about one order higher than that of non resonant values. This result indicates that PAV thin films will be effective for NLO device application. The incident light wavelength dependence of χ(3) revealed that as the wavelength decreases.4 x 10-10 esu at 1. MOPPV and PPV films.Handbook of Polymers in Electronics Figure 3. χ(3) increases. These values are non resonant χ(3) values and are almost the same as that reported for a processible polydiacetylene (n-butoxycarbonylmethyl urethane) (n-BCMU-PDA. respectively. 74 . and 7. dispersion measurements are required in the absorption energy range to clarify the nature of the resonance and to determine the maximum resonantly enhanced χ(3). X-ray diffraction patterns indicate that the PAV films have low crystallinity. Thus.85 x 10-11 esu. The evaluated three-photon resonant values of χ(3) of the PAV films are almost of the same order of magnitude as that of crystalline PDA films. respectively. The maximum χ(3) of PPV film. 500 and 420 nm for PTV.

The χ(3) values of amorphous and crystalline films of 4BCMU-PDA have been compared using THG measurements. At a wavelength near the two-photon absorbance. the value is expected to be almost the same as PTS-PDA. Soluble PDA. Using a degenerated four wave mixing (DFWM) technique with backward interaction geometry.5 x 10-11 esu.064 μm was obtained [23]. For these purposes a large non linear refractive index (n2) and processibility are two of the most important features. single mode channel waveguides of 4BCMU-PDA and 3BCMUPDA spun films have been fabricated.e. Minimisation of the loss is needed for actual device applications. Using this technique. Channel waveguides of PTS-PDA single crystal on a Si/SiO2 substrate have been fabricated by a photolithography technique [26].. The value of n2 in the PTS-PDA chain axis direction is found to be 3 x 10-11 cm2/W at 1. The orientation effect due to the crystallisation of the polymer is revealed to be approximately a factor of five.06 μm and that of the crystalline film is 5 x 10-11 esu [19]. Using this grating coupler. 75 . Using an inverted rib design.3 n-BCMU-PDA PDAs have been widely investigated as potential materials for all-optical switching devices. the χ(3) values of the spin coated film is about 10-11 esu at 1. directional couplers and grating couplers are fabricated. If the alignment of the polymer chain is attained. waveguide losses measured by the total waveguide throughput over given distances (longer than 1 cm) were revealed to be larger than 5 dB/cm for 0.064 μm. and a coupling efficiency of 45% at 1. There will be a considerable contribution from two-photon resonance in this system. The mechanism for the non linear index is thought to be phase space filling by excitons [25]. Using a pump and probe technique for measuring n2 of thin films of spun 4BCMU-PDA at 630 nm. χ(3) values of the red form and the yellow form of 4 μm thick 4BCMU-PDA film are revealed to be 4 x 10-10 esu and 2. This large loss may be due to non uniformities in film thickness and refractive index. which provides lateral confinement [21]. which are potentially attractive for applications in all-optical signal processing. Strong self-lensing effects have been observed through thin film slab waveguides formed with 4BCMU-PDA using a 1. Single-mode planar waveguides made from these films have propagation losses as low as 1 dB/cm. such as 4BCMU-PDA and 3BCMU-PDA are of special interest for the application of polymeric waveguides with high optical non linearity.65 μm thick film at 1.0 μm mode-locked Nd:YAG laser which provides single 35 ps pulses.06 μm. the real part of n2 is reported to be negative with a magnitude of around 6 x 10-12 esu. the large imaginary component of n2 dominates the response of the directional coupler [22]. i.Non Linear Optical Properties of Polymers for Electronics 3. The estimated value for n2 is approximately 10-13 cm2/W [24].3. respectively. Guided light is predominantly in the PDA layer with the glass channels. Assanto and co-workers fabricated an efficient grating guided-wave coupler using 4BCMUPDA slab waveguides. The difference of these values is explained to be due to a conformational transition from an extended rigid coil in the red form to a random coil in the yellow form [20].

processible main-chain polymers with different types of π-conjugation structure have been investigated. Jenekhe and co-workers reported an organic polymer superlattice using a soluble conjugated polythiophene derivative [30]. respectively. The response time of the polymer is said to be faster than the normal instrument response of 25 ps. From DFWM measurements in a phase conjugate geometry for the sulfuric acid solution of the polymer. For the experiment 250 mJ pulses with 25 ps full width at half-maxima were used. i.4 x 10-11 esu at 2.06 μm. The response time was less than 70 ps. They are easy-to-fabricate amorphous solids made by conventional spin coating or casting methods from solution. such as 3-alkyloxymethoxy thiophene or 3-methyl-4´octyl-2. 76 . the position of a threephoton resonance was revealed to depend on the concentration of the polymer [28]. In the case of the solution of the polymer in chloroform.5 Processible π-Conjugated Polymers Apart from typical π-electron conjugated polymers such as PAV. and heteroaromatic polymers. and a π-deficient aromatic ring that is alternately connected with a π-rich aromatic ring [33]. 3.4 μm. By using THG measurements.3. PT is of considerable interest because a sulfurcontaining heterocyclic backbone increases the rigidity of the polymer and hence the πelectron localisation. THG measured as a function of wavelength for poly(3MOT) is revealed to be 4. a χ(3) of 2. were investigated using DFWM at 1..Handbook of Polymers in Electronics 3. n-BCMU-PDA and PT. limited by the laser pulse width. a donor-acceptor structure in their π-electron conjugated unit [32]. which is soluble in common organic solvents.2´-bithiophene5. in the preresonant region [27]. Three types of main-chain polymers will be discussed: symmetrically substituted benzylidene aniline with chloride (SBAC) polymer. The main chains of these polymers possess donor substituents at both ends of their π-electron conjugated unit [31]. Waveguiding properties of the polymers were also investigated.5´-diyl (3MOT). Soluble PT is synthesised by adding alkyloxy or alkyl groups into a thiophene ring. They concluded that the short non linear response obtained with pulses less than 200 fs is derived from initial photogenerated excitons. which is about six times smaller than that obtained with 400 fs pulses [29]. The effective χ(3) is less when the excitation pulse duration is shorter than the relaxation time of the excitation which gives rise to the non linear response.e. Prasad and co-workers studied poly(3-dodecylthiophene) using a 60 fs pulse DFWM and obtained a resonant χ(3) of 5.5 x 10-11 esu at 660 nm.4 PT Among the class of π-conjugated polymers.7 x 10-7 esu at 532 nm was estimated. The NLO properties of poly(3-butylthiophene). azo-dye polyester.3. the wavelength dependence of χ(3) for these main chain polymers was investigated and the resonant enhancement of χ(3) revealed.

However. N-dibutylamino derivative of SBAC. between the excited states and enhance the molecular hyperpolarisability. The control of transition dipole moments by donor/acceptor substitution or heteroatom introduction into π-conjugated systems is an effective way to enhance the χ(3) of the materials. it is difficult to obtain thin films of the vacuum-deposited SBAC polymer with good optical quality. γ. The synthetic scheme for the SBAC polymers is shown in Figure 3. This idea is different from donor-acceptor substitution based on a two-level model. Figure 3.3 Transition dipole moment between the 1Bu and 2Ag excited states of SBAC A strong χ(3) enhancement of the vacuum-deposited SBAC polymer thin films was observed when the incident wavelength is three times the wavelength of the lowest energy peak in the absorption spectra. SBAC polymers are easily obtained by polycondensation reaction from terephthalic aldehyde and N. This three-photon resonant χ(3) reached approximately 2 x 10-10 esu. the SBAC molecule was combined with an alkyl chain or with 77 . As a result. P. SBAC is a benzylidene aniline derivative in which donor groups with nitrogen atoms symmetrically substitute both ends of the π-conjugated unit. such as the azo-dye polyesters. SBAC polymers were synthesised where SBAC molecules are used as a part of the polymer main chain [35].Non Linear Optical Properties of Polymers for Electronics SBAC polymer is a novel symmetrical molecule with a large χ(3). Even in the off-resonant regions. Therefore.4. the χ(3) of short π-conjugation molecules depends on dipole moment change between the ground state (G) and the 1Bu excited state due to the intramolecular charge-transfer effect from donor to acceptor. as shown in Figure 3. the χ(3) was 4 x 10-11 esu. This novel molecule was designed to control the transition dipole moment. The transition dipole moment between the 1Bu and 2Ag excited states is enhanced by symmetrical donor substitution of the relatively short π-conjugation of benzylidene aniline [34].3. In this donoracceptor system. These values are comparable to those of non crystalline or non oriented π-conjugated polymers.

Handbook of Polymers in Electronics Figure 3. Figure 3. the χ(3) values in the resonant region were evaluated. good optical quality thin films were obtained.4 SBAC polymer synthetic scheme an ester chain. The wavelength dependence of χ(3) of polyester SBAC(II-c) thin film is shown in Figure 3.50 to 0.60 μm) of the laser beam used here.5 χ(3) wavelength dependence of SBAC polymer (II-c) 78 . The maximum χ(3) value obtained is about 7 x 10-11 esu at 1.57 μm.5. All polymers exhibit χ(3) values of 10-10-10-11 esu in this resonant region. Since the SBAC polymers are soluble in organic solvents. Since SBAC polymers have an absorption in the third-harmonic wavelength region (l = 0.

but also in short π-electron conjugated systems like an azodye-introduced main-chain polymer by modification of molecular structure. The χ (3) spectrum of the polymer is shown in Figure 3. An intramolecular charge transfer derived from a substituted donor and acceptor also contributes to the increase of χ (3).7 along with its absorption spectrum. The polymer is polyester with N. it should be emphasised that a large χ (3) is possible not only in π-electron conjugated polymers.e. N-diethylaminonitroazobenzene introduced into its backbone. A mono-azo dye may easily be incorporated into the main chain of a polymer system. This is because the main-chain polymer has a very high dye density. The value thus obtained for the azo-dye-introduced main-chain polymer is very high even though the dye used is a short π-electron conjugation system (i.Non Linear Optical Properties of Polymers for Electronics In an azo-dye-introduced main-chain polymer. a two benzene ring mono-azo dye). χ (3) was of the order of 10-11 esu even for the four benzene ring π-electron conjugation system [32]. as recognised from its chemical structure. These main-chain polymers show promise for the development of processible materials with a large χ (3). Thus. the dye possesses an electron donor and an acceptor along the backbone (electric dipoles are arranged in a head-to-tail configuration) [36].. The polymer is soluble in common organic solvents and fabricated into a thin film using a spinning technique.0 x 10 -11 esu. For the polyimide (PI) system with π-electron conjugation units in the backbone without a donor/acceptor. The largest χ (3) is in the resonant region with a value of 2.6. A value of χ (3) larger than 10 -10 esu was achieved for an intramolecular charge transfer dye-attached three benzene ring polymer system [37]. The synthetic scheme of such a polymer is shown in Figure 3. Figure 3.6 Azo-dye-functionalised main-chain polymer synthetic scheme 79 .

8 Molecular structure of heteroaromatic polymers 80 .8. The charge transfer between heteroaromatic rings in the π-conjugated sequences is thought to influence certain excited states that contribute to the χ(3) enhancement. Their chemical structures are shown in Figure 3. and include polythiophenediyl-pyridinediyl (PTPY). PTPY. These heteroaromatic polymers are periodically sequenced copolymers with well-defined polar monomer units.Handbook of Polymers in Electronics Figure 3. The most important feature of these polymers is the intramolecular charge transfer from the π-rich rings to the π-deficient rings [38].7 χ(3) wavelength dependence of azo-dye-functionalised main-chain polymer A different type of processible π-conjugated polymer is a heteroaromatic polymer with π-rich (electron donating) heteroaromatic rings and π-deficient (electron accepting) heteroaromatic rings which are alternately combined to form the polymer [33]. polythiophenediylbipyridinediyl (PTBPY) and polyphenylenediyl-pyridinediyl (PPPY). in Figure 3.

where χ(3) values of PDTB are one order smaller than those of PTPY. Typical film thickness was 0. and elongation of the π-conjugation Figure 3.9.2 x 10-11 esu at the non resonant wavelength [39]. another type of heteroaromatic polymer with no π-deficient pyridine ring.4-di(2-thienyl)benzene). which contribute to the χ(3) enhancement.9 Synthetic scheme for PTPY 81 .5-diyl).25 and 2. which suggests the occurrence of an intramolecular charge transfer from thiophene rings to pyridine rings. PDTB. The orbital distortion through heteroatoms in the polymer breaks electron-hole symmetry to contribute to the χ(3) enhancement. The synthetic scheme of PTPY is shown in Figure 3. The existence of different heteroaromatic rings that induce the charge transfer interaction on the π-conjugated sequences was thought to influence the properties of certain excited states. This result. was reported to have a χ(3) value of 1.8 x 10-10 esu at 1.1 x 10-11 esu in the three-photon resonant region and a value of 0. shows a red shift of the absorption maximum compared with poly(thiophene2. The χ(3) value was four times larger than the resonance value of amorphous 3BCMU-PDA and was comparable to those for PPV and the promising π-conjugated polymers for optical switching application. The absorption and χ(3) spectra obtained for PTPY are shown in Figure 3. Usually. where hv is the photon energy of the fundamental wavelength and Eg is the optical band gap energy. The resonance χ(3) value of PTPY is larger than that of PTBPY. such as 1Bu and 2Ag.1 μm. The maximum χ(3) value of PTPY is 2. Dissolving the polymers in formic acids and spin coating on a glass substrate allowed amorphous polymer films to be prepared.10. These heteroaromatic polymers are synthesised by nickel(0) complex polymerisation as reported elsewhere [39]. In the off-resonance region. 3hv/Eg. the χ(3) value of π-electron conjugated polymers depends on the π-conjugation length. THG measurements of the polymer films were performed between 1.01-0. Poly(1.525 μm fundamental wavelength (hn= 0. A steep enhancement of χ(3) was observed at the fundamental wavelengths close to three times the wavelength of the absorption maximum.5-diyl) and poly(pyridine-2.3 μm. the χ(3) values for PTPY and PTBPY are larger than those of PPPY.813 eV). suggests that the orbital distortion due to the intramolecular charge transfer between the π-rich thiophene ring and the π-deficient pyridine ring enhances the non resonant χ(3).Non Linear Optical Properties of Polymers for Electronics particular. which has no π-rich thiophene ring.

Bipyridine units on the PTBPY polymer chain.0 eV for PTPY and PTBPY. respectively.8 at the near resonance wavelength corresponding to 3hv/Eg = 0. 3. polyurethane with symmetrical substituted tris-azo dye with fluorinated alkyl units (PSTF for short) was selected as a waveguide material. which are twisted more strongly than the periodic sequence of the five-membered thiophene ring and the six-membered pyridine ring in PTPY. This polymer is similar to the SBAC polymer family whereby a symmetrically substituted π-conjugated molecule was incorporated in a main-chain polymer. the χ(3) value for the (PTPY)/(PTBPY) system has been calculated to be 1. This value is consistent with the experimental value of 1.6 Third-Order NLO Polymer Waveguides Among the many types of processible NLO polymers.825.9.7 eV and 3. are considered to shorten the conjugation length and result in a decreased χ(3) value.3. Azo dye is an effective NLO dye investigated by many researchers and the tris-azo dye is very special for NLO applications. PSTF is a novel third-order NLO main-chain polyurethane with tris-azo dye incorporated into the main chain with a fluorinated alkyl backbone [40].Handbook of Polymers in Electronics Figure 3. Taking into account that Eg = 2.10 χ(3) wavelength dependence of heteroaromatic polymers sequence reduces the optical band gap energy. Fluorinated alkyl units are expected to be effective for reducing the polymer 82 . The χ(3) value has been reported to be proportional to the minus 6th power of the optical band gap energy.

3. The refractive index of the NLO polymers should be well controlled when single-mode waveguides are to be fabricated using the NLO polymers.3 μm reveals that it is a quasisinglemode waveguide. UV-cured fluorinated epoxy resin was selected. Pπ. copyright 1992.8 x 10-14 cm2/W [42].55 μm. where R represents fluorinated alkyl units.Non Linear Optical Properties of Polymers for Electronics Figure 3. This value was approximately an order of magnitude smaller than the value obtained by THG measurement.1) 83 . American Institute of Physics) waveguide loss. a buried PSTF waveguide was fabricated. is expressed as: Pπ = 3 λ A/4Ln2 (3. 44 to 66 mol percent. The non resonant χ(3) of the PSTF polymer film measured by THG was approximately 2 x 10–11 esu at 1. It has an appropriate refractive index for fabricating PSTF single-mode waveguides [41]. respectively. In this device configuration.11. This result was due to the strong two-photon absorption of the polymer at 1. an optical Kerr switch that uses the third-order optical non linearity of the material is a simple method to attain ultrafast response optical switching. From the result.11 Molecular structure of PSTF polymer (Reproduced with permission from [17]. of the polymer was calculated to be 2. As a cladding material. Although third-order NLO polymers generally have higher refractive indices than those of transparent polymers for the cladding layer.5 and 4. the PSTF has a moderate refractive index because of its fluorinated alkyl chain. The far-field pattern of the guided mode at 1. to the backbone polyurethane units.5 dB/cm. for the π-phase shift of the signal beam at the signal wavelength λ. The channel waveguide of the PSTF was fabricated applying standard photolithography and RIE techniques. By applying the UV-cured epoxy-cladding polymer on top of the ridge. switching gate power. in the NLO waveguide with the core area A. n2. the mask pattern was transferred to the photoresist and a ridge waveguide was fabricated through oxygen plasma etching. even though a fluorinated alkyl chain was used as part of the matrix polymer.55 μm were slightly large. the non linear refractive index. The chemical structure of PSTF is shown in Figure 3. and the medium length L.3 and 1. This was due to the high tri-azo dye content of the PSTF. By using a silicone negativetype photoresist and a mask aligner. The losses of the waveguide at 1. The non linear optical effect of the waveguide was also confirmed by detecting self phase modulation (SPM) of the waveguide at this wavelength.55 μm. With respect to optical devices using NLO materials.

3. or polyene-dye-functionalised polymers have been investigated as second-order NLO materials (χ(2) materials). This absorption limits the wavelength at which optical switching can be operated. For that purpose.Handbook of Polymers in Electronics It is important to switch optical signals with small gate power. stilbene-dye-. showing efficient NLO characteristics with low absorption loss [44]. In this case. To reduce the gate power. To realise the alloptical switching using polymer waveguides with less than 1 W switching power. Properties of Second-Order NLO Polymers 3.47 - Length >km 4 cm 1 cm (target) In the case of chalcogenide glass fibre with an n2 value of 2 x 10-14 cm2/W. the core area should be decreased.1.2 metre fibre [43]. a peak switching power of less than 1 W was obtained using a 3. The characteristics of all-optical switching materials and the required optical switching power for the materials are shown in Table 3.4. the polymer waveguide should have an n2 value two orders of magnitude higher than that of the PSTF waveguide or it must have one-order lower absorption loss as well as oneorder higher n2. Optical switching using the PSTF waveguide has not been attained so far owing to its strong linear and non linear absorption. a high electric field 84 .1 Azo-Dye-Functionalised. Much effort should be concentrated in developing NLO polymers with higher optical non linearity with low loss for all-optical switching with allied voltage similar to that of glass optical fibre switches.1 Characteristics of all-optical switching materials Sample SiO2 fibre Chalcogenide fibre PSTF *at 1.55 mm n2 (cm2/W) 3x10-16 1x10 3x10 -14 -13 Loss* (dB/m) 2x10-4 3 4x10 2 Switching power (W) 1 0. It is thus important to think about the trade-off between linear and non linear absorption and the χ(3) value of polymer waveguides when selecting the wavelength for optical switching. Table 3. Poled Polymers for Second-Order Non Linear Optics Azobenzene-dye-. or the medium length and n2 of the medium should be increased. the dye in the polymer should be aligned in a specific direction to possess second-order optical non linearity.4.

A nitro-terminated version of the bisazo dye derivative and a typical monoazo dye. respectively. 3RNO2. It has been revealed that β of the poled polymer increases rapidly with chain length if the molecular planarity of the dye is maintained and there will be no aggregation of dye in the polymer network [46]. dye-functionalised polymers are promising χ(2) materials. β. and 2RNO2. The molecular structure of 3RDCVXY is shown in Figure 3.e. The π-conjugation length dependence of the second-order NLO hyperpolarisability.. electric field poling is necessary to obtain χ(2) polymers. i. The non linear electronic polarisation of the dye-functionalised polymers originates from mesomeric effects that usually depend on the size of the π-conjugated systems of the dye.Non Linear Optical Properties of Polymers for Electronics will be applied to the dye-functionalised polymers. Figure 3. derivative is also discussed in [47]. These dye-functionalised polymers are easy to process as high-quality thin films for fabricating optical waveguides and a large χ(2) value (~10-7 esu) is easily obtainable. The polymer investigated here is a polymethylmethacrylate (PMMA) copolymerised with methacrylate esters of a dicyanovinyl-terminated bisazo dye derivative. Disperse Red 1 (DR1). These azo dyes are hereafter referred as 3RDCVXY.12 (a) Chemical structure of 3RDCVXY bis-azo dye (b) Chemical structure of deuterated 3RDCVXY polymer 85 . has been discussed by many researchers [45].12a. From these points.

The thermal and temporal stability make 3RDCVXY a viable substitute for the current inorganic electro-optical (EO) materials. The stability of these 86 . 100 and 80 °C for 3RDCVXY.0 x 10-6 esu.Handbook of Polymers in Electronics Each dye molecule contains a dicyanovinyl group or a nitro group as an electron acceptor. 3RNO2 and 2RNO2. This is caused by the χ(2) enhancement effect of two-photon resonance near the absorption band. LiNbO3. respectively. The 3RDCVXY and 3RNO2 dye contain three benzene rings connected with azo groups. and an ethylethoxyamino group as an electron donor. corresponding to the absorption spectrum. The χ(2) increases as the fundamental wavelength decreases. respectively.48 eV) and 470 nm (2. The methyl substitution of the 3RDCVXY was very effective for increasing the dye content in the copolymer and as a result the dye content was nearly 2 times higher than those of the 3RNO2 and 2RNO2. The glass transition temperatures (Tg) were 135. which were 500 nm (2. Figure 3. The poling direction was vertical to the film surface. respectively. 3R. It was revealed that the maximum χ(2) of the 3RDCVXY reaches 1.41 eV) for 3RDCVXY was longer than those of 3RNO2 and 2RNO2.13 χ(3) wavelength dependence of 2R. The maximum absorption wavelength of 515 nm (2. so their conjugated structure is longer than that of 2RNO2. The χ(2) was determined according to the standard procedure and its wavelength dependence is shown in Figure 3.13. This is 3 and 7 times larger than those of the 3RNO2 and a typical inorganic NLO crystal. This donor-acceptor charge transfer will greatly contribute to β. and 3RDCVXY polymers A thermal ageing test shows that the χ(2) of 3RDCVXY is stable even when kept at 80 °C for more than 6 months. These polymer films on glass substrates were poled using a parallel electrode poling technique.64 eV).

more than 5 orders higher than conventional liquid crystal optical devices or thermo-optical waveguide switching devices. By using the deuterated 3RDCVXY polymer.14 where standard photolithography and RIE is used. Deuteration or fluorination will be needed even for NLO waveguides. This polymer is composed of 3RDCVXY-attached PMMA and a transparent PMMA where all the hydrogen atoms are deuterated. Using an electric-field poling technique. A bifunctional molecule. and a half-wave driving voltage of 12 V of the interferometer was obtained [50].2 EO Polymers One of the important features of second-order NLO materials for obtaining optically active devices is an EO characteristic. efficient EO property with moderate absorption loss is attained. such as a molecule with an amino group and a (N-ethyl. Through this process. 87 . The selection of cladding layer is important to obtain flatness of the waveguide surface where the metal electrode for supplying the driving voltage will be deposited. the value should be increased to more than 40 pm/V to reduce the driving voltage with transistor-transistor logic (TTL) level. azo-dye-functionalised poled polymers are promising materials and have been investigated [49]. By using the deuterated 3RDCVXY polymer. 3.Non Linear Optical Properties of Polymers for Electronics EO polymers at high temperatures is an important area of NLO polymer research. The value is low compared to the LiNbO3 interferometer. a deuterated 3RDCVXY polymer was developed for device application. a vertical coupling MZ interferometer was also fabricated [51]. Nhydroxyethyl)amino group. It is necessary to fabricate channel waveguides with low loss to make NLO polymer devices such as phase modulators that can be driven with low input power. though it is possible to enhance the value by applying a higher poling electric field to the waveguide or by using a longer waveguide. For such applications. One way to increase the thermal stability of NLO polymers is a crosslinked polymer system where NLO dye is covalently attached to the polymer network at more than one site. its chemical structure is shown in Figure 3. From a practical viewpoint. To this end. The EO coefficient (r-coefficient) of the waveguide was 26 pm/V at about 70 MV/m poling voltage. is one example.12(b) [48]. EO polymer waveguide devices such as modulators and couplers are of special interest because response time faster than a nanosecond will be obtained using the device. which reacts with a trifunctional isocyanurate comonomer. These azo-dyefunctionalised poled polymers have the potential to be applied to a variety of optical devices due to their processibility and low potential. whose r-coefficient was approximately 32 pm/V. This polymer is reported to be stable at 75 °C for more than three months. a Mach-Zehnder (MZ) interferometer was fabricated. The waveguide fabrication process is shown in Figure 3. a channel waveguide was fabricated.4.

where two types of polymer core are aligned by using photolithography and RIE techniques.5 χ(2)) value of 80 pm/V at 1. Electric poling is necessary to make the polymer film NLO active.Handbook of Polymers in Electronics Figure 3. a channel waveguide structure is desirable.4. is an effective method for fabricating a QPM waveguide. This controllability made it easy to form a periodically aligned structure composed of a poled 3RDCVXY polymer 88 .14 Fabrication method for a core channel waveguide based on 3RDCVXY 3. To obtain high efficiency from the QPM devices. such as second-harmonic generation (SHG). Almost all the QPM devices reported to date use inorganic materials and there have been very limited reports on QPM frequency conversion devices using second-order NLO polymers [53].3 μm [49]. deuterated 3RDCVXY (as NLO and active part) and a UV-cured epoxy resin (as a transparent part) are used as a waveguide core. The fabrication process and fabricated polymer QPM waveguide structure are shown in Figure 3. The deuterated 3RDCVXY polymer exhibited a d33 (= 0. For fabrication of the QPM waveguide.15.3 Serially-Grafted Polymer Waveguides To realise frequency conversion devices by using a second-order NLO process. which is an important factor in realising high efficient frequency conversion [54]. Changing the fluorination content of the resin can easily control the refractive index of the UV-cured epoxy resin. the quasiphase-matching (QPM) technique is an attractive method as it is easy to achieve frequency conversion. A serially grafted waveguide fabrication technique. with high efficiency and to obtain a collimating light beam from the device [52]. This is because the latter are difficult to fabricate into a specific structure with precise periodic poling pitches.

53 dB/cm. This refractive index matching between two polymers is important to reduce the Fresnel reflection at the interfaces between two polymer cores. a low refractive index UV-cured epoxy resin was first spin coated as an undercladding layer of the waveguide.15 was used to fabricate the serially grafted polymer waveguide. Then. The Fresnel reflection loss of the grafted interface was 89 . Using this technique. the epoxy resin core ridge was fabricated using photolithography and a RIE process. On top of a silicon substrate. the NLO polymer in the waveguide was poled by supplying a high electric field by using parallel electrodes. This poling process provided large second-order optical non linearity only to the periodical parts of NLO polymer in the core layer.001. The process shown in Figure 3. respectively. After spin coating of the UV-cured epoxy resin on top of the NLO polymer core. this overcladding layer covered the groove under the NLO polymer core ridge that was formed during the fabrication of the serially grafted waveguide structure.67 dB/ cm and 0. The refractive index difference between the UV-cured epoxy resin and the NLO polymer was controlled to within 0. The periodic length (Λ) in the waveguide was controlled easily by changing the mask pattern for the photoprocess. a buried channel waveguide with periodic structure was fabricated by covering these core ridges with a low refractive index UV-cured resin.15 Schematic of polymeric QPM waveguide fabrication method and a UV-cured epoxy resin with almost the same refractive index. after fabricating a thin film layer of the NLO polymer and patterning it by photolithography. a QPM frequency conversion polymer waveguide was successfully fabricated. The loss of the NLO polymer and UV-cured resin of this QPM waveguide were 0.Non Linear Optical Properties of Polymers for Electronics Figure 3. Then. Finally. Although the oxygen plasma etching rates of these two polymers are different. a core ridge of NLO polymer was fabricated by an RIE process.

SHG experiments were performed with 5 mm long QPM waveguides using a colour centre laser with 1. A variety of polymer waveguide gratings have already been proposed [57. 58]. The QPM waveguide had an efficiency of 4x10-1%/W/cm2.4 Refractive Index Grating Fabrication into Azo-Dye-Functionalised Polymer Waveguides Waveguide grating (an important device in optical communication and signal processing systems) has functions such as input-output coupler. An azo-dye-functionalised polymer is one of the candidates for fabricating 90 .16 Relationship between laser power and SHG efficiency of the QPM waveguide (Reproduced with permission from [57]. The relationship between the applied voltage and the SHG intensity at the wavelength is shown in Figure 3.65 μm as fundamental wavelengths. The application of hybrid waveguides will be key in optical signal processing technologies. When the fundamental wavelength was 1.16. American Institute of Physics) 0. 3. wavelength filter and wavelength division multiplexer.4. By changing the periodic length. the phase-matched wavelength for SHG was controlled. the largest ever reported for a QPM polymer waveguide [56].Handbook of Polymers in Electronics Figure 3.48-1. in the 10 to 90 μm range at intervals of 1 μm. the SHG intensity was strongest in the waveguide with a periodic length of 32 μm. This hybrid waveguide fabrication technique can be applied for an optical sampling device and a compact all-optical switching device.005 dB/point [55]. copyright 1996.586 μm.

From the IR absorption measurement of the 3RDCVXY polymer film before and after laser irradiation. was attained using 3RDCVXY polymer thin film. 60]. a high output efficiency. The efficiency was monitored using a 0. Figure 3. In this case. Using atomic force microscopy.17 Diffraction efficiency of the grating with 1. the fabricated structure was not a relief grating but a refractive index grating. So.Non Linear Optical Properties of Polymers for Electronics gratings using the photochemical reaction of the azo dye in the interface region of two laser beams. By the two laser beam interference process using 532 nm light from SHG of a continuous wave (CW) Nd:YVO4 laser as a light source. This grating has a very thin relief structure. These surface relief gratings based on the isomerisation mechanism were optically and thermally erasable. it was revealed that 532 nm laser light could effectively induce the photobleaching of 3RDCVXY. 35% or more. the thickness of the relief structure of the film was evaluated to be about 30 nm. The second mechanism is irreversible photobleaching of the dye that occurs under higher energy irradiation. This reaction can be explained by following two mechanisms.6 μm spacing 91 . 60].17 [64]. The first mechanism is the reversible trans-cis-trans isomerisation of the dye where a strong interference beam was irradiated [59. as shown in Figure 3. a π-conjugated system in the azo dye is broken and a permanent refractive index change of the polymer occurs [61. 1300 nm and 1550 nm wavelengths. The refractive index changes of the film by photobleaching were measured at 633 nm. 62].5 mW 633 nm He-Ne laser by measuring the first-order diffracted light power. 830 nm. onetenth or less than those of typical surface relief gratings with the same diffraction efficiency [59. A surface relief grating can be fabricated through the movement of the azo-dye-functionalised matrix polymer through dye conformational change due to isomerisation.

respectively. about 80 μm in depth.500 and 1. and 0. and 0. and 1550 nm. respectively.466 for DR1(10%)/ PMMA and the UV resin.005. respectively.3 dB/cm. The refractive index difference (Dn) of the film before and after 20 minutes irradiation was 0.014. 0. 0. In designing and fabricating the grating. and the fibre was butt-jointed to the waveguide end face. A refractive index grating was formed in a DR1 (10%)/PMMA thin film on a glass substrate.Handbook of Polymers in Electronics The refractive index decreased with increase of irradiation time at each wavelength.005 at 633 nm. 0. The other method was grating formation on the buried waveguide through photobleaching by using two beam interference light from a 532 nm SHG laser.18. This loss was practically available for a few centimetres application of the waveguide. 1300 nm. An azo-dye-functionalised PMMA solution was spin coated into this groove. A Ge photodiode was used as a detector. two simple methods were applied [63]. To evaluate the optical propagation loss of the fabricated buried waveguide a cutback method was applied. A schematic of the waveguide endface cut by a dicing saw is shown in Figure 3.004 at 633 nm. then a UV-cured resin was spin coated on top of the waveguide.6 cm.022.2%. The light source and its intensity were the same as those of the 3RDCVXY photobleaching reaction.006.009. 92 . the combination of these simple techniques is an easier method than that of typical fabrication processes such as photolithography and RIE method. PMMA and DR1 were dissolved in chlorobenzene and the solution was filtrated through a 0. The change in refractive index of the film before and after 20 minutes irradiation was 0. To fabricate a waveguide grating. with a loss budget of ~3 dB/cm. PMMA containing 10 wt% DR1 (DR1(10%)/PMMA) solution was spin coated on the groove-shaped substrate.7 to 1. A periodical refractive index grating structure was fabricated onto this buried channel waveguide.3 μm laser diode was coupled to optical fibre. the loss was evaluated to be 1. 830 nm. Light from a 1. The refractive indices of the waveguide materials measured using a Metricon Model 2010 Prism Coupler at 1.005. and a buried waveguide of the azo-dye-functionalised polymer was fabricated. The refractive index decreased with increase of irradiation time at each wavelength measured. 0. A UV-curable epoxy resin of equal composition to the substrate was spin coated on this DR1(10%)/PMMA buried waveguide layer. 1300 nm. By varying the waveguide length from 0.2 μm filter. A channel waveguide was fabricated using the above-mentioned method.3 μm wavelength were 1. 830 nm.6 μm period and saturated after irradiation for 20 minutes reached 6. and 1550 nm. One was waveguide fabrication by using an etched groove of an epoxy resin substrate shaped by using a dicing saw. PMMA was used as a host polymer of the refractive index buried waveguide core and DR1 was added to functionalise this polymer. the core/ cladding of which was 50/125 μm in diameter. The thickness of the substrate was approximately 90 μm and the groove size was 41 μm in width and 44 μm in height. The diffraction efficiency of the grating with 1.

e. linear and non linear absorption.2%. These simple fabrication methods are widely applicable to a variety of polymer systems in which refractive index change can be induced by photobleaching. several technical problems exist in second. The polymer waveguide grating was fabricated by the combination of using a grooveshaped substrate for buried waveguide fabrication and a photobleaching technique for the grating fabrication. should also be considered. To address these issues. a refractive index grating was inscribed into the buried waveguide. time and grating period were the same as those for the thin film grating. a waveguide with the combination of a signal processing function of NLO polymer and a signal transmission function of a transparent polymer. The outputcoupled light angle was detected at approximately 70 degrees and the output-coupling efficiency was 10. the trade-off between χ(2) and χ(3) values of polymer waveguides. i. Hybrid waveguides can be fabricated by constructing the waveguide such that many optical functions are serially 93 . Irradiation intensity.3 μm laser diode light was coupled into the waveguide through optical fibre. and reliability should be carefully considered. The coupling efficiency was less than 1% because the waveguide surface flatness was not good. processibility. 1. To detect output-coupled light via the grating. novel hybrid waveguides. The input-coupling characteristic was also measured and the coupled light was detected at approximately 70 degrees.5 Future Targets of NLO Polymers for Optical Device Applications Currently.18 A schematic of the end-face of a buried waveguide By using the above procedure.and third-order NLO polymers. As mentioned above. output-coupled light angle and its intensity were measured.. By rotating a photodiode from the position perpendicular to the grating (0 degrees) to the end face where light comes out (90 degrees). 3. which was defined as the intensity ratio of light output from the grating to light from the end face.Non Linear Optical Properties of Polymers for Electronics Figure 3.

Chemla and J. Watanabe. a hybrid waveguide structure is proposed. Tamamura. Standard photolithography and RIE techniques were applied to fabricate the vertically integrated waveguides. 3. mainly focusing on the azo-dye-functionalised NLO polymers. Using the vertically stacked directional coupler. Acknowledgements The author would like to thank S. T. Amano. Springer-Verlag. 2000. M. To make the most of polymer processibility. Y. Shuto. Hattori and T. 3.S. Kaino.Handbook of Polymers in Electronics grafted or vertically integrated. Asobe. Volume 29. Nonlinear Optical Properties of Organic Molecules and Crystals. M. 1990. Journal of Optics A: Pure and Applied Optics. Hinton. Sasaki and T. 2. Germany. S.6 Conclusions NLO waveguides for optical switches and optical modulators have been discussed. The hybrid waveguide design can be applied not only for second-order NLO waveguides but also for all optical switching waveguides by considering the role of the integrated polymers. K. S. These hybrid waveguide fabrication techniques can be applied for EO waveguides and for χ(3) waveguides. References 1. Maruo. The vertically integrated polymer device fabricated to date was a vertically stacked second-order NLO polymer directional coupler [54]. These hybrid techniques may be extended to many types of functional device fabrication. Y. Journal of Lightwave Technology. D.. but also by optical system researchers. Zyss. Photonic Switching II. T. The successful development of polymeric optical waveguiding devices will require much effort not only by NLO material and device researchers. FL. 94 . Toda and H. 4. Orlando. Shibata for their contribution to the research work. 1718. Hikita. Springer Series in Electronics and Photonics. T. The non linear optical material used was a 3RDCVXY polymer. 2. Tomaru. Berlin. Kurihara. 1995. Ed. Academic Press. USA. T. 8.. It is anticipated that this new approach of the application of hybrid waveguides will be a key for future advances in optical signal processing technologies. Ed. 1987. 4. M. optical coupling characteristics similar to that of an in-plane directional coupler were obtained. 13. R1.

27. New York. Kaino in Polymers for Lightwave and Integrated Optics: Technology and Applications. 247. H. 2107. 53. S. I. L. No. Kobayashi. L. Chen and J. 1990. Yang. S. Ed. Hryniewicz. Noguchi and M.W. 1991. Marcel Dekker. Sinclair. Jenekhe. 1993. 26. Karasz and C.E. Electronics Letters. G. Vanherzeele and J. S. Murase. Lillta. Polymer. No. 125. 1992. 347. Sandman. Neyer. 1. DC. Moses and M. Tokito and S. 1337. 1988. 10.J. 1985. 1342. 11.H. S.P. S. T.C. A. Matsuura. Kaino. 12. USA..S. T.J. 29. Electronics Letters. Hall. Ohnishi.J. 21. 7. Burroughes. Eds.Non Linear Optical Properties of Polymers for Electronics 5. D. 12. Mori. Yoshimura and T. Electronics Letters. Spangler.. 16. R. 183. 6. K. T. S. 457.R. Sapochak and L. Kubodera and H. J.. Materials Research Society. T. Applied Physics Letters. Kajzer in Advances in Nonlinear Polymers and Inorganic Crystals. 1985 47. Imamura. Kurihara. S. H. Applied Physics Letters.K. Heeger. 17. Stucky and J. Tsutsui. 15. 18. and T. G.M. Murata. and Magnetic Properties of Organic Solid State Materials. 95 . Yamamoto.O. Washington. Y. Chapter 1. Garito and D. Chien. NY. 1993. 1979. C. 95. Hirooka. Chemical Physics Letters. Kurihara. 1987. F. Ed. M. 1986. Wnek. T. Ando.D. 19. Khanarian. Carter. S. Synthetic Metals. Volume 247. Matsui. 1992. Kubodera. K. S. American Chemical Society. C-J. PA. Meth in Electrical.E. Dalton in Nonlinear Optical Properties of Organic Materials III. S. Polymer Communications. ACS Symposium Series. A. 102.S. Materials Research Society Symposia Proceedings. 9. Hornak.E. 15. 399.V. Kanbara in Materials for Nonlinear Optics. T. Saito. Knoche and L. Y. T. 534. 455. 6..F. G.Y. 539.W. 5. J. L. Warrendale. 1990. Thakur. Musikant. Isawa. 8. Liquid Crystals and Laser Media.Muller. 1991. T. Havelka. G. Ed. Polis. No. 14.R. Marder. Sasaki and F. T. Ed. Chiang. Kaino. 1991. Sohn. T. 1441. G. T. Etemad and F. 13. 704. Nature.A. Baker. K. 29. 12. Proceedings of the SPIE. Proceedings of the SPIE.L.J. A. Kaino. T. USA. 362. Kurihara. 2002.W. A. 20. D. 824. Optical.

Applied Physics Letters. Krol and M. T.-H. Electronic Letters. Rao. 70. Krug. A.N. 11.R. D.J. R. S. M. Kurihara. 1992. 18. No. Jackel. Prasad in Proceedings of the SPIE. Jen.L.H. 33. Schelburne III and S. 2.E. 1990.L. M. Mori. Prasad. Jenekhe.L. 1147. 56. Kaino. Tomaru. Pan and P. T. 12.A. Walker. Blau and K. Journal of Applied Physics. Electronics Letters. T. 15. 4. H. T. 31. N. 17. 22. Applied Physics Letters.D. 21. Tomaru and T. P. Miao. 1993.L. T. Kurihara. P. 115. Jackel. Baker. 28. Nahata. 29. Chemical Matter. Kaino. Journal of Chemical Physics. J. Kanbara and T. 1990. J. 32. Burzynski and P. Etemad in Nonlinear Optical Properties of Organic Materials II. Schlotter. 7049. 28. 1990. D. 2341. 56. Oba. 13. 1989. 31. V.A. 319. Polky. 24. Macromolecules. Kaino. 1992. Stegeman. 126. Houlding. Q. 681.C. T. Darzi. G. J. 896. Townsend. T. Assanto.N. Townsend and G. 1406. Proceedings of the SPIE. Yadley and R. J. S. 1989. Matsumoto.N. Applied Physics Letters. 96 . 1990. Molecular Crystals and Liquid Crystals. A. Y. J. G. Japanese Journal of Applied Physics. Thakur. Y. Zhou. 84.I. 26.M. T. Yamamoto. 222.K. 169. 1. S. Z. K. 1216. 1990. W-C. 1986. Flom. Kurihara and S. Kurihara. N. 229. Nonlinear Optics. Derstine and J.Handbook of Polymers in Electronics 20. Chen. 1991.N. Prasad. 2201. T. 4. Switakiewicz and P. Byrne.L.D. Kaino and S. 32. 1. Y.N. Zanoni. Elsenbaumer. G. T. 1990. 34. 1990. Kaino. Synthetic Metals. R. A. 1990. No. S. 25. 27. Valera. Kurihara. W. W. Mori. Kubodera and T. E. P. Meyler. 23.-Y. Ghoshal. 26. 57. Journal of Chemical Physics. Chopra. 30. S. 256. 93. 1985. 182A. Baker. Tomaru. 35. 222. Lo and S. Thakur and S. Gong.

184. 251. K. M. Yaita and T. Amano. Y. H. Ed. 3. S. 1988. Tomaru. 1991. H. Dalton.S. Tokuda.F. Jager. Yokohama and T. L. Synthetic Metals. Dalton.E. Chiang. N. 43..G. 1901. T. M. Kaino. Marder and J. S. Kurihara. 97 .R. 61. Applied Physics Letters. 42. C. Tomaru. 170. Metallo-Organic. Kajzar. Sapochak and C. 1368. Xu. M. S. 1992. Chemical Communications.P. L. Electronic Letters. Journal of the Chemical Society. No. Shuto. M. IEEE Photonic Technology Letters. Kaino. K. Kuzyk. Cai. Zambori. L. in Organic. 1210.Y. Proceedings of the SPIE. T. I. 891. Lalama. 48. M. Y. Ttaliani and R. 1995. Mori. 54.R. C. 39. Zhou. 1990. Applied Physics Letters. J. Hikita.L. Bosshard. Ikeda. 1396.U.-H. 1993. 11. T. Comizzoli. Yamamoto and K. 1991. No. Amano and T.B. Singer. 1991. S. Y. 49. Sohn. 45. Journal of Adhesion. Y. Tomaru. L. Perry.W. 38. 223. Katz and M. Bosch. 1992. 1003. Zhang and L. 37. 1990. W. M. Kaino. I. 46. Applied Physics Letters. 76. Synthetic Metals. 32. MRS. 35. T. Hikita and T. M. 37. Maruyama. Nakamura. R. A. Ichimura. Yu. Nagatsuma. M. 515.D. Watanabe. Kanbara. T.. Sandman. Singer. C. F. Shuto.Non Linear Optical Properties of Polymers for Electronics 36. Amano and T. M.R. Applied Physics Letters. Liakatas. 47. Garito and D. Ruani. 44. Z. Yokohama. K. 19. Kurihara and M.E.1560. and Polymeric Materials for Nonlinear Optical Applications.D.J. M. 1994.. Volume 247. 68. Amano and T. Shuto. Materials Research Society Symposium Proceedings. 179. T. Eds. Amano. I.J. Schilling. Kaino in Nonlinear Optical Properties of Organic Materials IV. Proceedings of the SPIE. Kaino. G.2143. Eds. 2000. 156. 1996. Gunter. M. 67.R. Kurihara. T. K. Ohara. 41. M. S. Kaino. Asobe. Chemical Physics Letters. Kaino. Holland.Chen. 40. T. Pittsburg. Asobe. 1991. 53. 800. P. C. Tomaru and T. T. S. Murata. T.

54.Y. Yokohama. G. V. Kusyk. 1994. Donval. Eds. 1998. 2000. 1205. G. ED-25. Shuto. 1990. Feuer and D. 1998. 3796. M. 4179. M.K. Byer. T. 8835. Norwood.A. R. Haas. S. M. Applied Physics Letters. 31. T. 51. Journal of Applied Physics. 831. Shuto. 28. Rochon. 12. M. Amano. Applied Physics Letters. Tripathy. Tomaru. 57. S. 2000. 3240. M. 55.W. A. T. Applied Physics Letters. Onodera and T. 25. M. IEEE Journal of Quantum Electronics. T. T. Hong and A. Lee and S. W. Karim. F. Han.-C. M. C. S. 65. 28. T. Amano and M. 320.-H. 10. Amano.G. 13. Foglietti. 1996. Y. Ahn. T. No.M. Y. Applied Physics Letters. Amano. E. 2794. Eich and M. 1995. Y. Onodera and T. M. Kaino in Organic Nonlinear Optical Materials. X. 60. Tomaru. Hikita. S. T. S. IEEE Transactions on Electronic Devices. 26. 72. Proceedings of the SPIE. Fejer and R. Zyss. 1760. L. 1559. Bertolotti. Kaino and M. 72. Applied Physics Letters. M. Michelotti. E. Journal of the Chemical Society of Japan. Applied Physics Letters. 1989. M. 63. Khanarian. Onodera and T.L. Shibata. 1978. Kumar and S. T. 1161. Lee. Asobe. J. S. D. Barrett. V. Shuto. 87. Kim. H. D. Yariv. 68. 59. M.H. Electronics Letters. Shibata. 62. 9. Macromolecules. 977. Kaino. 1995. Tomaru and H. Watanabe. Kaino.L. Macromolecules. Hikita. Hattori. Watanabe. 58. P. Toussaere and J. Hattori. Petrocco.J.Handbook of Polymers in Electronics 50. 22. Oh. Yoshimura. 1451. M-S. Tomaru. B. 174. Shibata. A. 63. I.G. Hikita. M. Shivshankar. 1993. Kozawaguchi. 56. 7. 98 . Ho and C. Taggi. 53. 1995. Natansohn. 13. Hikita. 57.. Shuto and S. Lim. J. Jiang. 61. 1998. Y. 1193. Ng. R. Hattori. 52. Li. V.

such as decay kinetics.. Most of the significant features in luminescence studies have their origin in the fact that the electronically excited states are affected by molecular interaction and molecular motion. Since the fluorescence properties of a probe molecule. by reviewing and summarising the data already available in the literature.1 Introduction When radiation is incident on a material some of the energy absorbed by a chromophore is re-emitted as light of a longer wavelength. the fluorescence probe method can be used to probe the local mobility of polymer chains both in solution and in the solid state. the translation and segmental motion of a polymer chain are temperature dependent. due to photophysical features of polymers. However. which is dependent on segmental motion of the polymer chain. It is one of the purposes of this chapter to demonstrate. The frequency depends on the nature of the emitting states. Wandelt 4. the translational and segmental motions are very extensive but are much reduced in concentrated or bulk polymer systems. The intensity depends on spectroscopic selection rules: the efficiency of competing non radiative. The macromolecules that become expanded in a good solvent tend to contract in a poor solvent below the value of its unperturbed dimensions. quenching and energy transfer processes. It can also be applied 99 .e. defined by Flory [5]. that. That is important. There are many pathways for the deactivation of the absorbed energy. whether it is a singlet or a triplet state. so that the thermally activated dynamics of the polymer chain can affect the mobility of the probe molecule. i. fluorescence investigations are the methodologies suited to the study of environmental effects in a polymeric network. The photochemists [3. which is in agreement with Stokes law [13]. In the solution state. Fluorescence probe methodology can be applied for studying microstructures and the morphology of a polymeric medium [6-7]. 4] suggested classifying polymers to distinguish between those in which the repeat unit contains a chromophore and those in which isolated chromophores are attached to a polymer chain as an end group or minor component of a copolymer. Two important domains characterise the radiation: intensity and frequency. are strongly affected by microenvironments.4 Luminescence Studies of Polymers B. since the main deactivation processes are bimolecular complexes through dimer formation. and whether this is a complex formatted by an interaction with some other chromophore.

S1 and S2 are excited singlet states and T1 is the excited triplet state. ground-state and excited complexes) have been observed owing to the differences in the formation of molecular interaction between moieties of polymers. intersystem crossing (ISC). Some of these are unimolecular whereas others are bimolecular. latex beads [9]. with an emphasis on phase transition and phase separation studies. imaging processes.1 Jablonski diagram of the important unimolecular photophysical processes of excitation energy dissipation: absorption (A). The present review begins with a brief description of the basic principles of luminescence [1-3]. phosphorescence (P). S0 is the singlet ground state. one of which is in the excited state prior to complexation. 4. 100 . after which it deals with the fluorescence studies of polymers in solution and energy transfer in polymeric systems. Figure 4. Some of the unimolecular processes of energy dissipation following the absorption of light are depicted in a Jablonski diagram (Figure 4. Various fluorescent species (such as monomers. internal conversion (IC). Obviously the most important molecular probe in polymer fluorescence is an excimer: an excited complex of two identical species. fluorescence (F).Handbook of Polymers in Electronics in microheterogeneous systems. Spectral and time dependent studies of polymers in the gel state are discussed later. and only some of these will be discussed here. vibrational relaxation (VR).2 Basic Photophysical Deactivation Processes The excess of energy taken up by light absorption is known to dissipate through photochemical and photophysical processes.1). microlithography [8]. silica [10] and imprinted polymers [11].

k0. but in condensed phases these are more involved in photochemical reactions. However.1) Each process competing with the spontaneous emission reduces the observed lifetime. τ0. Obviously. so that the molecule relaxes to the ground vibrational level of the first excited singlet. ∑k i i is the sum of the rate constants 101 . of the fluorescence in the following way: τ0 = 1 k0 (4. which relates to the rate constant. are generally forbidden and require times from millisecond to seconds. which in turn are affected by temperature. If the spontaneous emission of radiation of the appropriate energy is the only pathway for return to the ground state. S1. relative to the natural lifetime: τ= 1 ( kF + ∑k ) i i (4. the average statistical time that the molecule spends in the excited state is called the natural radiative lifetime.Luminescence Studies of Polymers The initial absorption raises the molecule to an excited singlet state (S2). A mirror-image relationship usually exists between absorption and emission spectra. These processes. in times of the order of a picosecond. there will be higher energy singlet and triplet states. involving changes in multiplicity. T1. The relative content of all the processes is dependent on the molecular and supermolecular structure of the material as well as on the molecular motions. 4. the longest absorbed and shortest emitted wavelength usually corresponds to the 0-0 transition. The energy may then be emitted as fluorescence.2) where kF is the rate constant of fluorescence and for all processes competing with emission. τ. The triplet state may then lose its energy and return to the ground state either by emitting phosphorescence or by radiationless transition to the ground state or by ISC from T1 back to S1 when the energy difference between them is small enough to allow the thermal activation. the internal conversion (IC) between excited singlet states is usually very rapid. usually from the lowest vibrational level of the first excited singlet state to the ground state. or intersystem crossing (ISC) may take place to the triplet state.2.1 Luminescence Fluorescence is defined as the emission from a transition between states of the same multiplicity.

Spectral distribution of the delayed fluorescence is similar to that of ‘normal’ fluorescence. τP = 0 1 kP (4. determined from the absorption spectrum as a function of wavelength (λ): τ F = 10 −4 ε max ( λ ) (4. The radiationless processes from the higher to lower excited states are usually very fast. The measured fluorescence lifetime is usually less than the predicted value. This is attributed to the presence of quenchers like oxygen and many other impurities occurring at a concentration of about 10-3 M in the commonly used spectroscopic solvents. the natural lifetime.3) This equation predicts an approximate value of 10-9 s at εmax ≈ 105 l mol-1 cm-2. which may have quite different energies at their equilibrium geometries. τP . Before the molecule can react. encompassing vibratrional relaxation. However. its lifetime corresponds to the excited triplet state.1 can be approximated to a useful expression relating τ for a molecule to the maximum extinction coefficient εmax (λ). IC takes place as a transition between two isoenergetic vibrational levels of different electronic states of the same multiplicity. The lifetimes of the higher excited states are very short and quantum yields of emission from higher excited states are negligible. The natural lifetime can be formulated according to Equation 4. Fluorescence is a comparatively fast process and the radiative fluorescence lifetime is usually in the range of 10-6 to 10-12 s. The IC is used in a wider sense. of the triplet state is long. Consequently. It denotes radiationless transitions from the first excited singlet state into the vibrationally equilibrated ground states. the vibrational energy is quickly distributed among the various vibrations and can be partially or completely dissipated by collisions into heat. 102 . varying 0 between 10-6 s and seconds.4. Delayed fluorescence differs from ‘normal’ fluorescence in that the measured rate of decay of emission is less than that expected from the transition giving rise to the emission.4) Vibrational relaxation (VR) from a vibrational level of a higher electronic state such as S2 to the vibrational ground state is very rapid.Handbook of Polymers in Electronics Equation 4. Phosphorescence emission is the result of a transition between states of different multiplicity (typically T1 to S0) that has a much smaller rate constant than that for fluorescence.

IC and ISC processes are similar in that they involve a conversion of electronic energy into vibrational energy. This phenomenon of association of chromophores is called concentration quenching. and kIM and kIE are the rate constants for non radiative energy decay of the monomer end excimer. Additionally. respectively.2. respectively. As significant competition to radiation can come only from processes capable of occurring in the appropriate timescales. They only exist in the excited state and they dissociate into monomers upon radiative or non radiative deactivation in agreement with scheme shown in Figure 4. kFM and kFE are the rate constants of fluorescence emission of excited monomer chromophore and excimer. 4.Luminescence Studies of Polymers ISC differs from IC in that the transition takes place between states of different multiplicity as can be seen in Figure 4.2 Bimolecular Photophysical Processes Considering the excitation originating from the singlet ground state of a molecule. it may cause interaction of the excited state of a molecule with the ground state of the other. Figure 4. but the latter are of prime importance in a consideration of molecular motion and luminescence. respectively. which is followed by rapid relaxation to the lowest vibrational level of the lowest excited state. 103 . whereas phosphorescence can be significantly affected by a very wide variety of relatively slower processes.2.2 Birks’ scheme [1] of excitation and deactivation by bimolecular processes: kEM and kME are the rate constants of excimer association and dissociation. This may result in the energy transfer between the molecules. changes in fluorescence are likely to be caused primarily by the fastest molecular motions. Since the discovery of the pyrene excimer by Förster and Kasper in 1954 [12].1. there is a further possibility of energy dissipation involving the other molecule. The competition between the processes of energy dissipation can be controlled by either thermodynamic or kinetic parameters. which is able to interact with a similar or a different molecule. These all are known as radiationless processes. Excimers are complexes/dimers of electronically excited molecules with molecules of the same type in their ground state. resulting in the formation of an excited complex.

3 Quenching Processes There are many quenching processes.3 x 10-29 C m (10 D). Their fluorescence emission spectrum from the broad and structure-less band has been found to be shifted to the lower energy (relative to the molecular emission) by 50-60 nm. and kq is the quenching rate constant. It was shown by Beens and co-workers [13] that exciplexes from aromatic hydrocarbons and aromatic tertiary amines demonstrate the charge-transfer character of the complexes as reported by Knibbe and co-workers [14]. but their formation is not restricted to aromatic systems. If the sum of effective rate constants of the non radiative processes is so high such that the lifetime of emission is undetectable. in the absence and presence of acceptor respectively.Handbook of Polymers in Electronics these complexes were observed frequently with aromatic hydrocarbons. In complicated systems like polymers.30-0. if the crystal and/or material structure allow a close overlap of the molecular planes. includes self-quenching through excimers and exciplex formation. Rate constants for energy transfer can be measured by exciting a chromophore with a fast light pulse followed by monitoring the dynamics of the excited species. the exciplexes are polar entities. but there are other possibilities like quenching by electron transfer or by energy transfer due to presence of heavy atom. Photophysical quenching. 4. 104 . to the molar concentration of the quencher Q as: Φ0 = 1 + kq τ Q Φ [ ] (4. Quenching by photochemical reaction refers to organic photochemistry and will not be discussed here.5) relates the experimental values of the quantum yields of the process. Birks [1] and Klessinger and Michl [2] have given a more detailed discussion of the photophysics of organic molecules. Excimers of aromatic molecules adopt a sandwich structure with a separation distance of 0. The Stern-Volmer equation (Equation 4. and their dipole moments were greater than 3. Φ0 and Φ. The last photophysical process includes exciplex formation. Exciplexes are complexes of two different molecules usually of 1:1 stoichiometry.35 nm between them. which does not lead to a new chemical compound. Excimer fluorescence can be observed in solutions and in solids.2. which are non polar. It can be measured from the competition between emission and the deactivation by an added quencher or acceptor. and naturally both are important and interactive.5) where τ is the lifetime of the donor in the absence of additives. In contrast to the excimers. Their fluorescence phenomena are similar to those described for excimers. the competition between the possible processes is controlled by either thermodynamic or kinetic parameters. these molecules do not necessarily luminesce.

Among the several publications devoted to the methods of studies of time dependent fluorescence. There are essentially two types of methods for measuring fluorescence lifetimes: pulse fluorometry (relating to measurements performed in the time domain).Luminescence Studies of Polymers 4. respectively. where τn and Bn are the lifetime parameter and pre-exponential function of the nth component in the decay. The recorded decay curve of emission intensity. of molecules. of a process ‘i’ is defined as the number. and to probe local environments. they are used for many purposes. such as determination of reaction kinetics. The last-squares analysis uses a quantity χ2 as a measure of discrepancies between data and fitted function and. for a good fit. The data analysis software is used to extract the kinetic information in a given system from the experimental intensity decay curve. 105 .3. rates of competitive processes. a data acquisition system (consisting of timing electronics) and a data analyser (composed of a computer with re-convolution software). is generally synthesised by means of an exponential re-convolution function of the form: I( t ) = ∑B n n exp( −t / τ n ) (4. Birch and Imhof [16] have widely published on instrumentation design and analytical methods.. nA. 4.. Although the time-dependent studies of fluorescence pertaining to the fluorescence lifetime measurements are not sufficiently specific. Moreover.3. the spectral studies are widely used as analytical applications of fluorescence. I(t).6) with n = 1.2 Quantum Yields A useful quantity in the description of photophysical and photochemical processes is the quantum yield. and phase and modulation fluorometry (relating to the frequency domain) [15].2. it is usually recommended that the number of decay components chosen for least-squares analysis should always be the minimum necessary to give a satisfactory fit.3. 4.. Although fluorescence spectroscopy cannot be classified as a ‘finger print’ type. χ 2 less than 1.. the reader is referred to the book edited by Lakowicz [15].3 Methods for Fluorescence Studies The phenomenon of fluorescence spectroscopy contains two domains: spectral studies and time-dependent studies.1 Time-Correlated Single-Photon Counting Studies A single photon fluorometer consists of the following subsystems: an optical spectrometer (including a pulsed light source). An important feature of the equation is that the existence of n decay components suggests the existence of n excited states. The quantum yield.2 is recommended [16]. Φi.

They have a linear chain structure in which the substituents R and R´ are separated by three carbons. of light quanta absorbed [2]: Φi = nA Q (4. which says that if the chromophores are separated by 3 carbon atoms. of the singlet state are given by equations (4. Quinine sulfate in 1N H2SO4. 25 °C. ni. the quantum yield of fluorescence may be written as the ratio of the observed to the natural lifetime: ΦF = τ τ0 (4.2).Handbook of Polymers in Electronics A. ΦF = 0. the probability of excimer formation is the highest. assuming that the chain is flexible enough to rotate 106 .4 Fluorescence of Polymers. ΦF = 0. ΦF = 0. we measure the quantum yield relative to the quantum yield of a known standard compound. the vinyl polymers will be rich in excimer structures and strong bimolecular quenching of the fluorescence will occur.69 with λexc. If only processes that obey a purely exponential rate law such as fluorescence are involved in deactivating the singlet state. related to the number of molecules in a given state [2]: ηi = ni nA (4.7) For practical use.546 with λexc.9) where the natural lifetime.8) which is the ratio of the number. τ0. 4. This is in agreement with the Hirayama rule [20]. = 328 nm [18]. τ.60 with λexc. undergoing that process divided by the number.3. = 290 nm [19].1) and (4. If the substituents R are aromatic chromophores. nA. = 366 nm [17]. S1. of molecules undergoing a specific reaction to the number. It will be useful for many purposes to distinguish between quantum yield related to the absorbed radiation and efficiency. 25 °C. and the observed lifetime. Excimer Fluorescence The typical synthetic vinyl polymers prepared by the free radical polymerisation of vinyl monomers are shown in Figure 4. in the excited state. 2-Aminopyridine in 1N H2SO4. The following materials can be used as standards: • • • Rhodamine B in ethanol at 22 °C. ηi. Q.

This is almost entirely absent from these systems. the concentration of which will be the factor determining excimer fluorescence intensity. the polymer chains dissolved in fluid solution should have a Boltzmann distribution of suitable excimerforming sites. but it can have a transient existence when segmental motion and rapidly rotating chain backbones undergo a variety of conformation states. the conformation of the chain backbone required to bring neighbouring aromatic chromophores into sandwich geometry is one of unfavourably high energy. pyrene and carbazole. The vinyl polymers and copolymers that have been widely studied are: polystyrene (PS) [22]. This is because the rotational diffusion in the polymer chain can control the kinetics of the processes.3 Schematic representation of vinyl polymers with substituents R and R´ around the carbon-carbon bond. The emission characteristics of a solid-state polymer will then depend on the conformational equilibrium in solution existing at the temperature solidification. The aromatic chromophores have included phenyl. naphthalene. Excimer emission has been detected from a number of aromatic vinyl polymers [21-24]. as a relation between the ratio of excimer to monomer emissions 107 . According to this model. The majority of literature in polymer studies in the last two decades has originated due to excimer emission and formation. where the low-temperature distribution of chain conformations becomes trapped in a rigid medium. Harrah [25] has illustrated these dependencies for poly-2vinylnaphthalene. Therefore. Many photophysical processes in polymers depend on whether the process occurs in the solution or solid state. polyvinylcarbazole (PVCZ) [24]. A demonstration of this phenomenon in solid solutions of poly-2-vinylnaphthalene and poly-4-vinylbiphenyl. polyvinylnaphthalene (PVN) [23].Luminescence Studies of Polymers R' R' R' R' R R' = R' = R' = H H H R R= R= R= R H CH3 R R polyethylene (PE) polypropylene (PP) polystyrene (PS) O R' = CH3 R= C O R' = CH3 R= C O polymethyl methacrylate (PMMA) OCH3 polymethyl methacrylate (PMMA) Figure 4.

including the inter.1.Handbook of Polymers in Electronics and temperature of solidification. and the various photophysical processes occurring in polymers. and Ts is the temperature of solidification. has been shown by Frank and Harrah [26] in agreement with the following equation: ⎛ − ΔE E ⎞ IE ∝ exp⎜ ⎟ IM ⎝ RTs ⎠ (4.and intramolecular complex formation in terms of a singlet ground and excited states. The three routes of energy Table 4. The analysis of excimer and monomer emission in fluid systems is complex.11) where ΔEE represents the energy barrier between the normal and excimer creating conformations at the temperature at which the film was cast. is given in Table 4.1 Photophysical processes occurring in polymers Photophysical processes Energy absorption Fluorescence IC ISC Monomer quenching Phosphorescence ISC Singlet migration Excimer formation Excimer formation via preformed trap Excimer dissociation Excimer fluorescence ISC Non radiative process Excimer quenching 1 1 1 1 1 Initial species 1 Products 1 1 Rate constant Ia kFM kIM kTI kQM kPM kIT kMM kEM kEM kME kFE kIE kIE kQE M + hν 1 1 1 M* M M* M* M* M + hνFM 1 3 1 M* M* + Q 3 3 M + Q* 1 M* M* 1 1 1 M + hνPM M 1 1 M* + M M* + M 1 M + M* 1 (MM)* M* + 1(MM) 1 1 1 1 M + 1(MM)* 1 (MM)* (MM)* (MM)* (MM)* 2 M + 1M* 3 (1M) + hνFE (MM)* 2( M) 2( M) + Q* 1 1 (MM)* + Q 108 . A general kinetic scheme for excimer formation.

and/or the excitation energy can be transferred to an acceptor molecule. some competing radiative. As an example. as would be necessary in a solid. or it can migrate along the polymer chain. In many polymers. When two identical chromophores are brought into proximity in a suitable relative orientation. excimer emission.4. which can occur after singlet excitation in a polymer chain.Luminescence Studies of Polymers deactivation illustrated in Figure 4. migration. or by dimer chromophore. and then the energy migrates until the appropriate exciton trap appears. Energy quantum absorbed by the chromophore can be dissipated by single chromophore. and energy transfer processes. monomer emission. hνE. Figure 4. In a polymer chain containing a large number of chromophores. phosphorescence and non radiative transition. and represent the competitive relaxation processes if the system is unimolecular. Much of the evidence for energy migration comes from observations of excimer emission.1 are fluorescence. the intensity of excimer emission is greater than can be explained by absorption at the pre-formed sites. Among the many papers devoted to energy 109 . the exciton can migrate down the chain until a suitable trap appears or it can be transferred to a chemically different molecule (quencher). The explanation is that absorption occurs at monomer sites. there is a possibility that excitation energy may move as an exciton from one to the other by a non radiative process. and neither by conversion of the absorption site to excimer geometry by conformation change of a flexible chain. transfer and migration processes which can occur after singlet excitation. are shown in Figure 4.4 Schematic illustration for competing radiative. There are further possibilities involving both the molecules. The situation becomes rather more complex when bimolecular interactions are included. hνM.

1 Effect of Conformation of the Polymer Chain In solution.1.4. 33].4. can be controlled by either thermodynamic or kinetic parameters.12) I E = kFE I a kEM M ( kM + kEM M + kQMQ )( kE + kQEQ + kME ) − kEM MkME (4.14) Application of these equations and the scheme of photophysical processes to fluorescence observed under variety of conditions have been used in a number of papers on processes in polymer solutions and in solids [3.Handbook of Polymers in Electronics migration studies. The latter are of prime importance if we consider the molecular motion in the polymer. 4. 24]: I M = kFM I a ( kE + kQEQ + kME ) ( kM + kEM M + kQMQ )( kE + kQEQ + kME ) − kEM MkME (4. Somersall and Guillet [27] observed delayed fluorescence. as shown in Figure 4. The competition between the photochemical processes in polymers. involving 110 . 24. 28] studied photophysical properties for naphthyl-substituted polymethacrylate (PNMA) solutions very extensively.13) From the practical point of view. The various photochemical processes occurring in polymers and the related rate constants are given in Table 4. 23. the ratio of monomer to excimer intensity has been used very frequently: I M kFM ⎛ kE + kME + kQEQ ⎞ = ⎟ IE kFE ⎜ kEM M ⎝ ⎠ (4. inserting a stationary-state of excited monomer and excimer allowed the following expressions for monomer and excimer emission intensities (IM and IE.1. Since IM = kFMM* and IE = kFEE*. The spectral properties of absorption and emission of PNMA studied using different solvents under different conditions are shown in Figure 4. Guillet and coworkers [27.1 Fluorescence of Polymers in Solution 4.4. a wide description of particular mechanisms of energy migration and energy transfer can be found in [3]. but the most important factor in the case of a polymeric system is the chain conformation and flexibility.5. the rate of the many bimolecular photoprocesses due to a polymer chain may be limited by the rate of mutual diffusion of the interacting species. respectively) to be obtained by David and co-workers [23.

In Figure 4. with a lifetime of 0. 219. Somersall and co-workers [27] studied the fluorescence behaviour of polynaphthyl methacrylate in different solvents and they have shown that the ratio of excimer to monomer emission varied with the solvent quality. as illustrated in Figure 4. changed from 1.6. or a non polar solvent (such as cyclohexane). (3) and (4) delayed emission in tetrahydrofuran-ether at 77 K and phosphorescence (Reprinted with permission from Macromolecules.81 when the viscosity decreases from 0.184 x 10-3 to 0. American Chemical Society) the triplet state. (2) fluorescence. Cozzens and Fox observed delayed fluorescence in glassy PVN [29]. the ratio.6. 2. one can observe an increase in the ratio of emission intensity from excimer to monomer bands when PNMA was in chloroform and then cyclohexane was added to a 1:1 mixture of the solvents. Aspler and co-workers [28] demonstrated that the fluorescence properties correlate with a change in the effective volume of the random coil in solution.1 s.5 Ultraviolet absorption and emission spectra of polynaphthyl methacrylate in chloroform at 298 K: (1) absorption. An increase in excimer emission was observed if a non solvent was added to the solution to compress the polymer random coils. when the solvent is ethyl acetate. copyright 1973.125 x 10-3 N s m-2 [28]. 1973.44 to 2. These observations did not depend on whether they used a polar non solvent (such as alcohol). a mirror image of the absorption band due to monomer emission and a broad band shifted about 60 nm to longer wavelengths which is attributed to excimer fluorescence. The relationship between the fluorescence and viscosity was explained according to the classical Flory theory [5] of intrinsic viscosity: 111 . being visible with benzene as a solvent. However. monomer emission almost disappears and the excimer emission rises. IE/IM.Luminescence Studies of Polymers Figure 4. When chloroform is used as a solvent for PNMA. the monomer emission is predominant. These studies provide evidence for complicated chromophore interactions involving the excited states. Similarly. being high in poor solvents and low in good solvents. when PNMA in tetrahydrofuran-ether glass at 77 K was excited at 313 nm. Fluorescence spectra of PNMA at 298 K contain two main bands.

ρ. The average density of polymer segments. (3) in chloroform. American Chemical Society) [ η] = 63 / 2 φ < S2 > 3 / 2 φ < h2 > 3 / 2 or [ η] = M M (4. σ. copyright 1973.1 x 1021. is proportional to M / < S2 >3/2 and the relationship is: ρ∝ 1 [ η] (4.6 Fluorescence of PNMA in different solvents at 298 K: (1) in benzene. Chain length is important in providing a sufficient 112 .16) The rigidity of the chain has been characterised by the value of the steric factor. The intensities of the spectra are not comparative (Reprinted with permission from Macromolecules. 1973. (4) in chloroform-cyclohexane (1:1).17) where < h2 >f is the theoretical distance between chain ends with completely free rotation around all carbon-carbon bonds. 2. 2. < h2 >1/2 is the root mean square end-to-end distance and M is the molecular weight.15) where ø is constant. 221. which is defined as: σ2 = < h2 > < h2 > f (4.Handbook of Polymers in Electronics Figure 4. (2) in ethyl acetate. and < S2 > is the mean square radius of gyration.

(3) 279 K. range 1. The conformation of a polymer chain can be affected by the temperature of the polymer solution.400-6.7 Fluorescence spectra of poly(phenyl methacrylate) in THF. (7) 318 K: Excitation at 265 nm.16 can be used to explain molecular weight effects on excimer formation as a chain densification effect. Equation 4. (5)295 K. density and dipole moment measurements by Wandelt and Szumilewicz [31]. 113 . (4) 289 K.000.Luminescence Studies of Polymers number of chromophore interactions in intramolecular excimer formation behaviour. (6) 308 K. The conformation change of poly(phenyl methacrylate) (PPMA) in tetrahydrofuran (THF) solution was observed in dilute solutions using fluorescence emission. The fluorescence spectra of PPMA in THF solution when the temperature rises from 266 K to 318 K is shown in Figure 4. viscosity. Similarly. 4. at different temperatures: (1) 266 K.000 to 360.000 on increase of excimer emission. We can observe the shift of the maximum Figure 4. Aspler and co-workers [28] observed the influence of molecular weight of PNMA in the range from 40.8 x 10-3 M. (2) 273 K. Nishijima and co-workers [30] found a strong effect of molecular weight on increase of excimer formation when they studied low molecular weight polyvinyl naphthalenes series.7.

Handbook of Polymers in Electronics of fluorescence from λmax ≅ 335 nm to emission centred at λmax ≅ 358 nm. The emission spectrum of PPMA becomes very broad at 295 K where two bands are visible and comparative. Similar behaviour of fluorescence spectra was observed by Somersall and co-workers [27] for other methacrylate polymers PNMA, for which the monomer emission is relatively strong in comparison with vinyl polymers under the same conditions. The fluorescence emission spectrum of PPMA at 266 K fits 80% of the fluorescence spectrum of phenyl methacrylate, as is shown in Figure 4.8. Abuin and co-workers [32] reported similar fluorescence spectra in phenyl-containing methacrylate polymers solutions in ethyl acetate and in dichloromethane. As a first approximation, the phenyl chromophore in PPMA can be considered as isolated, because these polymers do not conform to the Hirayama 3 carbons rule. But we can observe considerable excimer emission from other polymers where the chromophores are separated by more than three atoms, for example in the spectra of naphthyl-containing methacrylates by Somersall and co-workers [27]. The spectrum of PPMA obtained at 318 K fits the Gaussian distribution function, as is shown in Figure 4.9, which would suggest that the majority of emission is excimer emission. Although the monomer and excimer bands from PPMA are strongly overlapping, the bands are distinguishable. The steric factor values obtained from viscosity studies [31] correspond to the values obtained for polyvinylcarbazole which was established as a stiff polymer [23, 24]. These studies emphasise the role of chain conformation and excimer binding energies in determining the extent of excimer formation. PS and PVN are examples of polymers where excimers can exist at nearly every point of the chain and the concentration of excimer sites could be quite high, especially when the mobility of

Figure 4.8 Fluorescence spectra of poly(phenyl methacrylate) in THF, 4.8 x 10-3 M, at 266 K (1) and of phenyl methacrylate in THF (2)


Luminescence Studies of Polymers

Figure 4.9 Fluorescence spectrum of poly(phenyl methacrylate) in dilute solution in THF, 4.8 x 10-3 M, at 318 K (1) and the fitting Gaussian curve (2)

the chain allows the necessary rotation to form an excimeric structure. Naphthyl esters are polymers where the probability of adjacent excimer formation is low and the high intensity of excimer emission would be due to the high efficiency of energy migration. The effect of temperature on excimer formation in a polymer chain is mostly due to thermally-activated conformational changes in the polymer chain. It was established that in dilute polymer solutions the singlet excimer formation is an intramolecular process since the ratio of excimer to monomer emissions intensity is independent of polymer concentration [23, 24]. However, it was shown by David and co-workers that in vinyl polymers, excimers usually occur between neighbouring chromophores and their formation is activated by temperature. Starting from 77 K, the intensity of excimer fluorescence from vinyl polymers is initially constant when it is in the glass state, and then increases, whereas the monomer intensity decreases. This is due to the fact that the rate constant for excimer dissociation, kME, is much lower than the rate constant for excimer formation, kEM, in the low temperature range. At a temperature higher than 202 K, excimer dissociation is very efficient for the vinyl polymers, and the intensity of excimer fluorescence decreases. This observation corresponds to a minimum which was observed by David and co-workers [23, 24] at 202 K in a graph of ln(IM/IE) versus 1/T. Values of energy of activation of excimers formation in poly-1-vinylnaphthalene and polyacenaphthylene in methyl tetrahydrofuran (MTHF) solution, obtained by David and co-workers [23, 24], were respectively 11.3 and 3.4 kJ mol-1. But the energy value of 14.7 kJ mol-1 was reported for activation of excimer formation in poly-2-vinylnaphthalene in solution by Al-Wattar and Lumb [33] and 15.1 kJ mol-1 by Harrah [25]. Chandross and Dempster [34] reported values of energy activation 13.8, 16.8 and 12.6 kJ mol-1 for


Handbook of Polymers in Electronics excimers association in, respectively, 1,3-bis-1-naphthylpropane, 1,3-bis-2naphthylpropane and 1-methylnaphthalene. The fluorescence behaviour of PVCZ solutions is quite different from that of the other vinyl polymer solutions. The emission spectrum of PVCZ results from two distinct excimers: a low-energy sandwich type structure with emission centred at 420 nm and a high-energy excimer centred at 375 nm. Itaya and co-workers [35] have proposed that the high-energy excimer has a structure in which only one pair of phenyl rings from the two-carbazole chromophores overlap. In the temperature-dependent curve for ln(IM/IE) as a function of 1/T, two minima corresponding to the formation and dissociation of two excimer structures were observed for PVCZ by David and co-workers [23, 24]. These two different excimer emissions have been assigned to different conformations of the chain, and a change in the conformation occurs between 143 and 295 K. Further information on these structures was obtained with use of time-resolved fluorescence spectroscopy. Time-resolved fluorescence spectra for PVCZ in benzene obtained by Hoyle and co-workers [21] are presented in Figure 4.10. This experiment showed that the high energy excimer, in a partially eclipsed form, appeared at the earliest times of observation,

Figure 4.10 Time-resolved fluorescence spectra of polyvinylcarbazole, 5 x10-4 M, in degassed benzene at 296 K, excitation wavelength 313 nm. Spectra obtained with time intervals from the lamp maximum: (1) 0-0.23 ns, (2) 8-9.4 ns, (3) 19-35 ns, (4) 182323 ns. Spectra are adjusted to the same intensity scale. (Reprinted with permission from Macromolecules, 1979, 5, 957, copyright 1979, American Chemical Society)


Luminescence Studies of Polymers (i.e., at a 0.2 ns interval from a photon absorption) and the emission from the lowenergy sandwich excimer was absent at that time. The low-energy excimer due to the normally eclipsed form appeared after 8 ns to be present after 182 ns as well. These studies suggest that the chain of PVCZ requires significant rotational time to form the sandwich excimer. The PVCZ chain was reported [23, 24] as a stiff polymer for which the steric factor from Equation 4.17 was 2.8, whereas it was 2.2 for PS [23, 24], and has a dielectric segmental rotational relaxation time of about 180 ns for a chain of Mw greater than 4 x 104 [36]. An interesting experiment was done by Cuniberti and Perico [37]. They synthesised a number of monodisperse polyethylene oxide samples terminated with pyrene groups. This experiment, which was related to the cyclisation of the polymer chain as it is schematically presented in Figure 4.11, showed that intramolecular excimer fluorescence increases inversely proportionally to the molecular weight of the polyethylene oxide chain separating the two chromophores. Similar experiments were continued by Winnik and co-workers [38] and they obtained the particular rate constants for cyclisation for PS and polydimethyl siloxane chains terminated by pyrenes. The cyclization activation energy, 14 kJ mol-1, was three times lower than that for excimer dissociation, 44 kJ mol-1, in pyrene-labelled PS. The difference corresponds to the binding energy of the excimers for solution of pyrene in cyclohexane, but approximate calculations have shown that the probability of cyclisation is strongly sensitive on the length of PS chain separating the two chromophores forming the excimer [38, 39]. It was shown that the addition of non labelled PS to pyrene-labelled polydimethyl siloxane reduces the rate of cyclisation. These effects were interpreted in terms of the decrease of the conformational mobility of pyrene-labelled polydimethyl siloxane chain through interaction with PS molecules.

Figure 4.11 Intramolecular excimer formation through end-to-end cyclisation of polymer chain


Handbook of Polymers in Electronics It has been demonstrated that the excimer emission intensity from chromophores incorporated into the vinyl polymer chain have been correlated with a change in the effective volume of random polymer coil in solution, and the volume of random polymer coil was correlated with viscosity, which is dependent on temperature. But a temperature change of a polymer solution does not always lead to expansion or contraction of the chain coil; it can cause conformation change to a more or less packed polymer chain and to a more or less excimer forming conformation. Both of these structural changes in a polymer chain can affect the fluorescence, but each polymer needs to be considered individually. Energy Transfer and Migration
The energy transfer and migration processes play an extremely important role in the photochemistry and photophysics of polymers. But, there is no direct measurement that allows conclusions to be made about these processes. Three types of energy transfer can be distinguished. Firstly, there is a transfer from the chromophore absorbing the incident radiation to the photochemically active site. A second type is collisional energy transfer, where the electronic excitation energy localised on the absorbing chromophore is transferred to another group on the same or different molecule as a result of the overlap of electronic charge clouds which occur during a collision. As an indicator of energy transfer efficiency we can use the Smoluchowski equation [3]:
kq = 4πrAB DAB 10 3


where rAB is the energy capture radius and DAB = DA + DB is the diffusion coefficient for relative movement of energy donor and acceptor. The third type of energy transfer takes place by resonance transfer over an extensive range of space, as a result of dipole-dipole interaction, as was proposed by Förster [40]. Migration of energy along polymer chains can occur by two mechanisms. When the electronic interactions between adjacent chromophores are weak, and the orientation correlations are low, the energy undergoes a statistical sequence of jumps from one chromophore to another as schematically shown in Figure 4.4. Each of the jumps has the characteristics of non radiative resonance transfer as proposed by Förster [40] and Dexter [41], and characterised by an effective energy diffusion distance. When there are strong interactions between neighbouring chromophores, and orientation correlations are appropriate, the energy may be delocalised as a wave over a number of chromophore units. The most convincing quantitative evaluation of down-chain energy migration comes from efficiency of polymer luminescence quenching by acceptor species present in concentrations which would be most inefficient if the absorbed energy were localised.


Luminescence Studies of Polymers When a system contains two fluorescing chromophores such that the emission spectrum of the donor overlaps the absorption spectrum of the acceptor, excitation energy from the donor can be transferred to the acceptor over a considerable separation distance, R. The efficiency, E, of this energy transfer would be governed by the equation proposed by Förster [40]:
6 R0 6 R0

+ R6


where R0 is a characteristic distance for a rotationally averaged pair for which half of the excitation energy is transferred. This characteristic distance depends on the overlap integral between the emission spectrum of the donor and the absorption spectrum of the acceptor [40]. There is always uncertainty if we adopt this equation for polymeric systems; the most important consideration seems to be the inhomogeneity of the polymer solution when the polymer segments are constrained into local high and low concentrations by the distribution of macromolecules. An incident photon absorbed by a chromophore is then transferred to the site of chemical activity. This is frequently followed by chain scission reactions, which in photooxidation depends upon the solubility and diffusivity of oxygen and the onset of localised molecular motion in the solid state [42-44]. To protect the polymer from the photooxidation and photodegradation, some additives are frequently used. Kryszewski and co-workers [45, 46] presented fluorescence intensity and lifetime studies as indicators of the efficiency of energy transfer between two polymers: PS and poly-2,6-dimethylphenylene oxide (PPO) and correlation between energy transfer and photochemical stabilisation. Thus transfer of energy from PS to PPO can be seen in Figure 4.12 in the diminution of PS monomer emission at about 285 nm, and the replacement of PS excimer emission with a maximum at 330 nm by PPO emission with a maximum at 315 nm. Overlap of the PPO emission with PS emission makes estimates of energy transfer from intensity measurements unreliable; time-resolved studies of fluorescence decay and resulting lifetime data have been used for this purpose. The decay curves have been fitted by two exponential function in agreement with Equation 4.6. The fluorescence lifetime data of the mixture of PS with PPO in solution are presented in Table 4.2. We can observe emission from both PS excimer and PPO. The τ1 = 12 ns due to pure PS in solution decreases with PPO increase and the relative intensity of the short-lived PPO component increases in the presence of PS. The decrease in the lifetime of PS subjected to Stern-Volmer analysis gave the slope 5.2 x 103 l mol-1. Semi-quantitative analysis, assuming the mutual diffusion coefficient of 2 x 10-11 m2 s-1, gave the distance of interaction in the order of magnitude 103 nm. Quenching efficiencies of this magnitude would be possible only


Handbook of Polymers in Electronics

Figure 4.12 Fluorescence of polystyrene quenched by poly-(2,6-dimethyl-pphenylene oxide) in tetrahydrofuran at 298 K, PS concentration 2.7 x 10-3 mol l-1 (styrene units): (1) no PPO, (2) 0.43 x 10-4, (3) 0.83 x 10-4, (4) 4.3 x 10-4, (5) 1.74 x 10-4, (6) 2.61 x 10-4 mol l-1 (Reprinted from Polymer, Volume 23, M. Kryszewski, B. Wandelt, D.J.S. Birch, R.E. Imhof, A.M. North and R.A. Pethrick, Photo-energy transfer in polystyrene-polyphenylene oxide blends, 926, copyright 1982, with permission from Elsevier Science)

Table 4.2 Lifetime parameters of PS in tetrahydrofuran at 298 K, concentration 2.9 x 10-3 mol l-1 of styrene units, quenched by PPO; λexc. = 265 nm, λem. = 330 nm
PPO concentration (10,000 mol l-1 of monomer units) 0.00 0.24 1.30 2.00 3.80 12 (no PS) τ1 (ns) 12.0 11.3 8.4 6.4 4.9 τ2 (ns) 1.1 1.2 1.1 1.1 0.9 χ2 0.9 1.3 1.5 1.6 1.2 0.9


Luminescence Studies of Polymers if the donor energy is effectively available over the whole of the PS chain coil and all the monomer segments of the PPO chain are able to quench the excited PS. However, studies of fluorescence in the solid state of the system [45] have shown that energy transfer from PS to PPO is efficient in the solid blend, and at 15 wt.% of PPO, almost all the emission is from PPO. However, the magnitude of PS stabilisation in the presence of PPO, calculated by analysis of the polymer chain scission processes of the polymer mixture in solution, is smaller than it would be from the energy transfer characteristics by fluorescence lifetime measurements. This suggests that chain scission arises from energy more localised than the mobile excitons in the quenching of fluorescence. Jensen and co-workers [47] reported that the decrease in PS excimer fluorescence is greater than can be explained by absorption of PPO at the excitation wavelength. Kryszewski and co-workers [46] showed the molecular compatibility of PSPPO blends is important. After studies of the fluorescence intensity and fluorescence lifetime measurements during storage and annealing of the polymers and blends, they suggested that annealing and storage permit chain packing rearrangements that favour non radiative energy conversion and transfer processes, and in the case of blends lead to the PS to PPO transfer which quenches the PS emission and photodegradation. Amrani and co-workers [48] have used fluorescence measurements of energy transfer from donor to acceptor for studies of polymer compatibility. They labelled methyl methacrylate-ethyl methacrylate copolymer and/or methyl methacrylate-butyl methacrylate copolymer with donor-naphthalene and polymethyl methacrylate with acceptor-anthracene. The variation in the ratio of donor to acceptor fluorescence was plotted as a function of butyl methacrylate and ethyl methacrylate in the copolymer and gradual increase of the ratio corresponded to gradual transition from two-phase to a one-phase system. The fluorescence technique was found to be more sensitive to small changes of compatibility of the polymers. Winnik [49] used fluorescence measurements of transfer of the electronic excitation between donor-naphthalene and acceptor-pyrene chromophores attached to the same polymer chain for studies of thermoreversible phase separation of aqueous solutions of poly(N-isopropylacrylamide) (PNIPAM). Dilute solutions of the doubly labelled polymer PNIPAM were heated from 277 K to 313 K, and the fluorescence emission intensity of pyrene (integrated spectrum) was measured when the system was excited with 290 nm, donor excitation, and when excited with 328 nm, acceptor excitation. Non radiative energy transfer between excited naphthalene and pyrene occurred in aqueous solution of the polymer. The increase in intensity of pyrene fluorescence when the solution was excited at 290 nm, shown in Figure 4.13, is due to a phase separation process at lower critical solution temperature (LCST). When the LCST was reached, the phase separation into polymer-rich and polymer-lean phases occurred. It was concluded that the collapse of the polymer chain leading to densification of polymer phase is followed by domination of intramolecular contributions to the energy transfer process.


Handbook of Polymers in Electronics

Figure 4.13 Plot of pyrene emission intensity as a function of temperature for aqueous solution of poly-(N-isopropylacrylamide) (PNIPAM) labelled with naphthalene(N)-donor and pyrene(Py)-acceptor; PNIPAM-Py/366-N/50, 44 ppm in water. Wavelength excitation at 290 nm due to N excitation, at 328 nm due to Py excitation (Reprinted from Polymer, Volume 31, F.M. Winnik, Phase transition of aqueous poly-(N-isopropylacrylamide) solutions: a study by non radiative energy transfer, 2132, copyright 1990, with permission from Elsevier Science)

4.4.2 Fluorescence of Polymers in Gel State Effect of Chain Conformation on Excimer Emission
Excimer formation can be explained in terms of a combination of local rotational isomeric and longer range diffusional motions of the chain. In polymer solution we observed and discuss the role of both; in solid film any type of movement is generally restricted, and the mobility of a polymer in a gel state is rather between the solution and solid, a more precise description of which was published by de Gennes [50]. The freely-rotating chain of a polymer in dilute solution is represented by a statistical distribution of conformational structures of the chain. The resultant excimer fluorescence emission is a broad Gaussian band. The excimer fluorescence spectrum from a solid polymer results in a very broad spectrum which is characteristic of the distribution of conformations adopted by the polymer in the preparation process. This distribution depends upon the thermal history of the sample and the conditions used for the casting; these dependencies were presented by Frank and co-workers [26]. The complexity of photophysical processes accompanying the excimer formation and the inherent complexity


Characteristic three-fold helical conformation of the chain and spherulitic morphological forms were observed by infrared spectroscopy and microscopy [7]. 50]. Some amount of short-lived component in the parameters fitting the fluorescence decays from crystalline iPS correspond to some presence of monomer emission.Luminescence Studies of Polymers of polymer systems (e. and the resulting photophysical parameters of the decays are shown in Table 4. The fluorescence emission spectra from the 68% crystalline iPS. this lifetime parameter does not change with the wavelength.6. and the crystalline iPS band is shifted a few nm to the red. i. We can observe similarities of the decays obtained for the 330 and 350 nm wavelengths of emission they are both due to excimer emission.15. A solution of iPS in benzyl alcohol (BA) quenched from 443 K to 273 K. 54]. The sample showed 68% crystallinity obtained from differential scanning calorimetry (DSC) thermograms. gathered in Table 4. which strongly overlaps the excimer band. A two-exponential fitting function was used for fluorescence decay from the crystalline iPS sample. The long-lived component of 21 ns is in the majority.3. additionally it is not photoactive in the region of PS excimer emission [51]. both excited at 257 nm are shown in Figure 4. with a rate of 0. 54].. more than 80% of the emission intensity is due to the component. which can easily be converted to the three-fold helical conformation by annealing at a temperature higher than the Tg [52.42 K s-1.e. One can see that the emission band from crystalline iPS is narrower then that of atactic PS. However. There is evidence for homogeneity of the excimer structures in the crystalline polymer.g. leads to the formation of a gel [51]. and from atactic PS (aPS) film cast from chromophore. tacticity) together with the conformational sensitivity of the structures make for analytical problems. Examples of time-resolved fluorescence decays from the crystalline iPS are shown in Figure 4.3. The iPS chain of the fresh gel exists in the extended conformation defined by Atkins and co-workers [52] and Sundararajan and co-workers [53. homogeneous helical conformation of the vinyl polymer chain.. especially if we compare the data with the same from aPS film.14. we can stimulate some of the local movement by photo and/or thermal cure [6. between 383 to 393 K. Some differences in the decay can be observed for emission wavelength 310 nm. Considerable changes in the excimer lifetime parameters and their 123 . was found to be necessary to fit the fluorescence decay from aPS film. Isotactic polystyrene (iPS) in the gel state was used by Wandelt [7] to obtain a selected. For some purposes. The sample of crystalline iPS was obtained from iPS/BA gel by heating at 293 K in the presence of nitrogen. where possibly some monomer emission at the shorter time of the decay was collected. The recorded decay curves of emission intensity from the crystalline and atactic PS were analysed using a non linear least-squares analytical method [16]. A three-exponential function. in agreement to Equation 4. BA appeared to be a good solvent for the gel formation and transparent in the infrared regions where the characteristic absorption of the helical conformations occur.

15 Fluorescence emission decays of crystalline iPS with excitation at 257 nm and different emission wavelengths: (1) 310 nm. Correlation of photophysical parameters with conformational structure of crystalline iPS and comparison with data of atactic PS. Volume 32. copyright 1991. excitation wavelength 257 nm (Reprinted from Polymer. 2708. B. Wandelt. copyright 1991. (2) 330 nm. with permission from Elsevier Science) 124 .Handbook of Polymers in Electronics Figure 4. with permission from Elsevier Science) Figure 4. Volume 32. B. 2709. (4) lamp pulse (Reprinted from Polymer.14 Steady-state fluorescence emission spectra of crystalline iPS obtained from gel and atactic PS film cast from chloroform at room temperature. Wandelt. (3) 350 nm. Correlation of photophysical parameters with conformational structure of crystalline iPS and comparison with data of atactic PS.

6 19. but the processes of preparation.7 16. The excitation energy can effectively migrate along the helical structure [60.18 1.9 9.4 21.e. i.1 54.3 5.7 11.5 39.3 35.3 2. Basically.9 6.Luminescence Studies of Polymers Table 4. because the fluorescence decay curve reflects not only the polymer type and solvent.7 31.2 12.4±0. In this situation. in the region of the lamellar borders.4 1.0 43.09 τ1 (ns) τ2 (ns) τ3 (ns) B1 (%) B2 (%) B3 (%) χ2 contributions with emission wavelength were observed in the case of aPS.8±0.3 21.99 1. The aPS film was cast from chloroform solution at room temperature.9 13.4±0.4.11 1.6 2.5±0.1±0.0 93.5 30.3 21.7±0.. the phenyls do not form excimer states.g.3±0.9 30. 63] to the lamellar border.8±1.4±0.8 53.8 1. This suggests that the excimeric band is very complex..5±0.22 1. quality of the solvent.1 90.2 41.0±0.4 21. This distance is too large for excimer formation of the sandwich type (which have a distance of 0.0±1.9 4.3-0.0±0. because the distance between parallel phenyls in the three-fold helical conformation is 0.2 27.6 8.3 Fluorescence decay data for 68% crystalline iPS and for aPS λem (nm) iPS 310 320 330 340 350 aPS 310 320 330 340 350 1. in the extended conformation as well as in the three-fold helical conformation of the iPS chain. The lifetime data of PS differ from laboratory to laboratory.2 19.4 29.4 4.23 3.665 nm.7±0.1 48. etc.6±0.8 83.9 15.5 51.9 72.2±0. where 125 .9 13.9 32.2 16.1±0.1 1.6±0.2±0.3 2.2 14.8±0.3 88. e. temperature.2 20.35 nm). Some examples of fluorescence lifetime measurements for PS from different laboratories are gathered in Table 4.3±0.16 0. the excimer can be formed only outside the crystalline region.27 1.3 7.27 1.19 1.6±0. because in these areas some deformation of the helical conformation of the PS chain makes the excimer structure formation more probable. as reported by Natta [62] and Sundararajan and co-workers [54]. and it included microstructural domains with frozen polymer chains of different conformations.2 15.6±0.3±0.3 5.4 12.1±0.

3 <1.Handbook of Polymers in Electronics Table 4. 4. The gel was formed by cooling a solution of iPS in BA (0%-20% w/w) from a temperature of 443 K. in PVN [64.3 χ2 Reference 55 55 55 56 56 56 57 58 59 59 60 61 61 the pre-excimer sites are formed.02 18. 24]. 333 Lifetimes (ns) 1. However.0 15. at a maximum cooling rate of 0. which lead 126 . 360 253.5 <1 15. 290 257.7 22.2 0.42 K s-1.9 15. to 273 K. for example.2 Effect of Phase Separation and Collapse Transition The phase separation process was observed in iPS gel [66.4.4 PS lifetime data from different laboratories Physical state of PS solution solution film solution solution solution solution solution solution solution Mw = 3.3 0. 330 255. 385 255. 360 250.5 17 21 1.6 1. 365 266. 270 257. 340 257. can explain the 10 times higher excimer emission from the crystalline state than from the fresh gel of iPS (extended conformation of the chain) [51].9 2. λem (nm) 266.2. only high effectiveness of energy migration would explain the strong increase of the excimer fluorescence emission from the crystalline iPS in comparison with the amorphous aPS observed by David and co-workers [23. 365 257.72 13. 65]. 290 257. 285 266.2 15. 333 253.85 17.0 14.800 solution oligomers solution solution Solvent CH2Cl2 CH2Cl2 CH2Cl2 toluene toluene toluene CH2Cl2 CH2Cl2 C2H4Cl2 C2H4Cl2 cyclohexane C2H4Cl2 CH2Cl2 λexc.3 4.3 <1. 67].5 1. only higher effectiveness of the energy migration in the three-fold helical homogeneous conformation than in the extended conformation. in which clear solution is obtained. Although the energy migration coefficient in PS is lower than.5 4 <1.3 12.

Annealing allows the iPS chains to undergo phase separation into PS-rich regions. which can be transformed into a crystalline phase with a characteristic. characteristic morphological structures were observed using polarised optical microscopy and a crystallinity value of 23% was obtained from DSC thermograms [66]. Changes in the lifetime parameters with emission wavelength suggest that the excimer emission band is rather complex and more than one type of excimer structure may be contributing to the emission spectrum. The rate at which this process occurs depends upon the temperature and time used. for which a two-dimensional view of the structure is similar to a fish net.5 together with the same for freshly prepared gel. Moreover. but it corresponds to the freezing of a certain number of degrees of freedoms [50]. polymer-rich and lean phases) may occur [50]. In the case of the iPS/BA system.. It is not an equilibrium process. There are no strict physical parameters in such a system.16. at the emission wavelength 340 nm. The phase separation step is determined at a fixed concentration by two factors: temperature and time. The lifetime parameter of about 26 ns in amount over 43%. and hence.Luminescence Studies of Polymers to a meta-stable state in which the chains adopt an extended conformation [52-54]. phenyl-solvent interactions are unfavourable in comparison with intramolecular phenylphenyl interactions. After annealing for 30 minutes at 318 K. thus under any weak and finite stress the crosslinks will eventually split. Under these interactions. gelation is conceptually similar to a glass transition. Then the polymer chain structure in the polymer-rich regions can be converted to the more stable form. in this case. red-shifted side of the fluorescence band. Generally. and the long-term behaviour of the material will always be liquid-like.e. some segregation into small regions high in chain concentration and others which are solvent rich (i. We consider a gel to be a series of chains which are associated by a physical process and where the crosslinks are not strong. The fluorescence emission decays of a sample of iPS annealed for half an hour required two exponential functions to obtain a good fit of the experimental curve. Thus. a polymer gel is a network of flexible chains. three-fold helix conformation [7. the BA is a poor solvent for iPS. The change of the steady-state emission spectrum of iPS gel during annealing at 318 K over a period of 30 minutes is shown in Figure 4. reported to be 323 K [52]. The annealing measurements were carried out at 318 K. This temperature was chosen because it lies sufficiently close to the Tg. it has been found [51-54] that the solvent plays an important role in determining the conformational structure of the gel. The photophysical parameters obtained at a series of wavelengths are presented in Table 4. and the same lifetime of 19 ns (if we take into account the error for 127 . 52. The changes observed indicate an increase in the intensity of a red-shifted excimer emission with time of heating. with respect to temperature or time of the process. 54]. and allows effective production of the heterogeneous two-phase system. For comparison the lifetime parameters of the freshly prepared gel suggest clearly that one type of excimer structure is present: similar contribution at the emission wavelengths 330 and 350 nm. shows that the long-living components of the decay correspond to the less energetic. but it is filled with solvent.

5 11.4 68. copyright 1991.26 iPS gel after 30 min of annealing at 318 K both emission wavelengths).5±0.19 τ1 (ns) 8.15 1.5±0. (3) 9 min. 5144. 24.5 11.3±0. If the quenching process of the pre-gelled solution is comparatively fast (of the order of minutes) the elimination of 128 . It was suggested by Atkins and co-workers [52] and Sundararajan and co-workers [54] that the extended conformation of iPS chains exists in the fresh gel and that it is stabilised by the solvent.3 18.6 60.4 80.3 12.5 31.9 43.2 χ2 1. (6) 30 min (Reprinted with permission from Macromolecules. (5) 20 min.4±0.6±1.98 1.16 Changes of the fluorescence emission spectrum of iPS gel (10% w/w) with time of annealing at 318 K: (1) 0 min. American Chemical Society) Table 4.6 1.4 39.6±0.5 hour at 318 K λem (nm) 310 330 340 Fresh iPS gel 310 330 350 5.1 56. (2) 4 min.35 0.8 18. 1991.9±0. (4) 14 min.Handbook of Polymers in Electronics Figure 4.4 τ2 (ns) 18.2 81.6 19.2 25.6 B1 (%) 59.9±0.3 5.6 24.3±0.5 Fluorescence decay parameters for iPS gel annealed for 0.8 B2 (%) 40.2 18.5±0.6±0.2 19.7±0.17 1.

with a fluorescence lifetime of 27 ns. Changes in the lifetimes for excimer emission at the red side of the spectrum (at 330 and 350 nm) are shown in Figure 4. a fluorescence lifetime of 29 ns is achieved.Luminescence Studies of Polymers solvent cannot occur and the polymer is frozen in a themodynamically non equilibrium state. the excess of solvent is expelled from the polymer chains.20) 129 . When the polymer chain undergoes the volume phase transition. The long-lived fluorescence excimeric structure vanishes after longer periods of storage and a majority of component of 20 ns can be observed after 864 hours.17 Dependence of the excimeric fluorescence lifetimes of iPS gel on time of storage at 283 K: (1) from emission decays at 330 nm and (2) at 350 nm: Excitation at 257 nm. curve 2. Figure 4. The rate at which the conformational transition occurs will depend on the conditions of the gel. After 528 hours of storage.2) can be rewritten: τ = ( kf + kn )−1 (4. The equation for observed lifetime (Equation 4.17. the gel exhibits an emission spectrum that contains a red-shifted excimer component. After 400 hours of storage. This suggests that the long-living excimer component is due to an unstable transition state. Density measurements of the iPS gel during the volume phase transition were performed and correlation with the fluorescence lifetimes for the long-term storage process of the iPS gel at 283 K was presented by Wandelt and co-workers [67].

The latter appears to be responsible for the lifetime changes. suggests correlation of the band with a short-lived component in the excimer spectrum. A high-energy excimer band with a maximum at 325 nm obtained with no delay after excitation and with a time interval of 9 ns can be identified with one phase. shown in Figure 4. Wandelt. Volume 33. The red-shifted emission band with maximum at about 345 nm in Figure 4.Handbook of Polymers in Electronics where kf is the fluorescence rate constant (which is independent of temperature). From measurements of time-resolved emission spectra for iPS/BA gel stored for 240 hours. it may be concluded that two phases exist in the system.18 Time-resolved fluorescence emission spectra of iPS/BA gel stored for 240 hours at 283 K. copyright 1992.S. The lifetime increase accompanies the decrease of the non radiative deactivation rate constant at around 400 hours of storage. (2) 6-11 ns. with permission from Elsevier Science) 130 . R.18 was obtained using a time interval of 79 to Figure 4. slit width = 20 nm. A close correspondence of the band with the steady-state fluorescence spectrum from the fresh gel. (Reprinted from Polymer.18. λexc. the same spectrum was obtained with time interval from 6 ns to 11 ns. 3561. Time-resolved excimer fluorescence studies as a probe of the coil collapse transition and phase separation in isotactic PS/BA gel. (3) 79-152 ns. and kn is the rate constant of the radiationless processes.=257 nm. Imhof. when the new redshifted excimer emission appears. Pethrick. R. Birch. the dotted curve.E.J. dotted curve is steady-state fluorescence spectrum for iPS/BA gel after preparation. D. B.A. obtained with time intervals: (1) 0-9 ns.

corresponds to spectra 1 and 2 in Figure 4. Time-resolved emission spectra shown in Figure 4. Spectra obtained with time intervals: (1) 0-5 ns. After longer times of storage.17. The band 2 with a maximum at 330 nm. (3) 71-149 ns (Reprinted with permission from Macromolecules. a model iPS gel was prepared [51] by placing a crystalline. with a maximum at about 325 nm. The high-energy band 1 obtained with no delay from excitation pulse. American Chemical Society) 131 . due to different excimeric structures in an iPS gel. which was immediately quenched to a solid gel. the red-shifted excimer structure of lifetime 29 ns was transformed into an excimer structure of lifetime 20 ns. corresponds to a short fluorescence lifetime. which is characteristic for polystyrene in solution. is due to an excimer structure clearly identified as characteristic for crystalline iPS [7] of 21 ns lifetime. obtained at a time interval of 7-16 ns. To observe the three time-resolved bands. and it can be ascribed to the polymer-rich phase. This red-shifted band appeared after phase separation into polymer-lean and polymer-rich phases. obtained with time interval 0-5 ns. as seen in Figure 4. previously nucleated material into a hot solution of iPS in BA. 1991. 5144. This band.19 indicate the existence of three excimer states.19 Time-resolved fluorescence emission spectra for modelled fresh iPS gel with suspended crystalline material. 17 ns.Luminescence Studies of Polymers 152 ns. (2) 7-16 ns.18. 24. This was completely invisible after 240 hours of storage but it was observed [67] after 744 hours of storage when the Figure 4. Copyright 1991.

60(comp.S. curve 1 was calculated in agreement with Equation 4. the steady-state fluorescence emission spectrum of iPS gel after annealing for 30 min at 318 K as curve 2.E.19.2 and comp.5 has been used to predict the theoretical spectrum for the two-phase excimer emission [66]. The time-resolved spectrum of the component 2 was shown [66] to be the same as the steady-state fluorescence spectrum of the 68% crystalline iPS gel. Figure 4. Volume 33. comp. The total intensity in Figure 4.3) is shown as curve 1.19. Birch. with permission from Elsevier Science) 132 .A. B. (Reprinted from Polymer. Wandelt. represented by band 2 in Figure 4. Imhof and R.20.3 correspond to spectra 2 and 3 in Figure 4. Correlation of steady state and time-dependent studies of a two-phase iPS gel.19 was obtained with a time interval of 71-149 ns. 3556.19 pertains to the crystalline material suspended in the last step of gel preparation having a memory of chain conformation.2 + 0.21. with a maximum at about 345 nm. The red-shifted fluorescence component was identified as an unstable excimer structure which finally undergoes transformation into a stable excimeric structure with emission at 330 nm. A linear combination of components 2 and 3 using the pre-exponential parameters obtained from the analysis of the decay at 330 nm emission wavelength in Table 4. D. copyright 1992.J.Handbook of Polymers in Electronics polymer chain was transformed to the three-fold helical conformation. Pethrick.20 The spectrum estimated using the equation I = 0. Figure 4. The band (3) in Figure 4. R. and is due to the redshifted excimer fluorescence of 29 ns lifetime.40(comp.

19.20 indicates that differences are observed at short wavelength due to the monomer and to some degree the extended conformation contributing to the spectrum. Thus the two-phase system excimeric fluorescence can be calculated: IE (two-phase) = IE (1) + IE (2) (4. The generally good agreement obtained in Figure 4.57 nm long. The two-phase model describes the results of the experimental studies of photoenergy migration in heterogeneous solid-state polymer blends by Frank and collaborators [68. It is worth considering that the emission arises from not only different states but also different phases. The generally good agreement between the theoretical and experimental curve supports the assumption that the excimer emission arises from a two-phase system.6(comp. but the three-fold helical conformation of the chains ensures that the parallel phenyl groups are separated by a distance of 0.21) where comp. Investigation of the fluorescence emission from the crystalline iPS shows that it is very effective. The structure of the crystalline phase favours exciton energy migration along the helix to the lamellae boundary 133 . The assumptions of the two-phase model are: • • There is no energy transfer between the different domains. Comparison of the experimental and theoretical curves in Figure 4. The distance between phenyl groups is large for excimer formation.4(comp. but the very regular and periodic chain microstructure incorporated into the lamellar macrostructure gives the chance for efficient energy migration.665 nm [54] and packed into a lamellar structure about 0. and The exciton can migrate inside a particular phase but becomes trapped at interfaces without escaping. The two-phase photophysical process described by Wandelt and co-workers [66] was similar to that previously used for a single phase [3].22 supports the model assumptions.2) + 0.20 between the experimental spectrum and that arising from the two-phase model calculated by Equation 4. and the processes are simultaneous and independent. Description of the excimer photophysics for a two-phase system presented by Wandelt and co-workers [66] are based on both the two-phase model assumptions and the experimental results.2 and comp.Luminescence Studies of Polymers IE = 0. This was compared with the experimental spectrum of the annealed iPS gel.3) (4.3 corresponds to spectra 2 and 3 in Figure 4. Tao and Frank [69] used three-dimensional electronic excitation transport to interpret the ratio of excimer to monomer fluorescence for poly-2vinylnaphthalene with polycyclohexyl methacrylate. contributions which are not included in the theoretical curves.22) where 1 and 2 refer to particular phases. 69].

134 . with a simulation by a superposition of three components (377. They concluded that the LCST implies a complete disruption of the ordered microstructures. then again shifts to shorter wavelength during a complicated crystal-crystal transition around 200 °C. It has been established [7] that all of the chromophores associated with the crystalline (and only 20% of those in the amorphous) state participate in the excimer emission. The decrease of lifetime with temperature seen in Figure 4. 71]. An interesting application of fluorescence studies was reported by Huang and co-workers [73]. They observed an increase in the fluorescence lifetime of the probe with increase of acetone content in the solvent. monomer emission was observed.20 and is involved in the complicated phase transitions of LC polyimides.Handbook of Polymers in Electronics where it is finally trapped in the interface region.21. In the initial time region. It shifts slightly to a shorter wavelength below the Tg and then shifts to a longer wavelength around crystallisation. and around the phase transition from crystalline to smectic phase at 240 °C. The temperature dependence of the complex fluorescence peak wavelength is shown in Figure 4. It was also concluded that these apparent changes in wavelength of fluorescence and lifetime behaviour are dependent on temperature and indicate the complexity of the nature of intermolecular complexes and radiationless deactivation processes in various phases of the thermotropic LC polyimides. then a decrease to a constant value at 319 K. with incorporated dansyl group and pyrenyl probe were reported by Hu and co-workers [70. An Arrhenius-type plot for changes in fluorescence lifetime of the complex during heating is shown in Figure 4. Picosecond fluorescence studies were applied by Winnik and co-workers [72] for studies of temperature-induced phase transition of pyrene-labelled hydroxypropylcellulose (HPCPy) in water. Temperature dependence of the fluorescence emission ratio of excimer to monomer emission (IE/IM) showed a significant increase of excimer emission in a temperature range 283-313 K. 398 and 421 nm). which were created in cold water. Fluorescence studies of volume phase transition of polyacrylamide (PAAM) in mixed acetone/ water solvent. They observed only one excimer emission above the LCST and that was with a maximum at 470 nm. The lifetime decreases with temperature until the Tg after which it slightly increases to again decrease gradually with temperature until the material reaches the smectic phase. They studied intermolecular complex formation between mesogenic terphenyldiimide moieties of a thermotropic liquid-crystalline (LC) polyimide (P-11TPE). with a maximum at 470 nm and a lifetime of 68 ns. They reported that gradual increase of fluorescence lifetime accompanies the volume phase transition of the PAAM gels from the swollen to collapsed state with increasing hydrophobicity of the microenvironment.22. Two excimer bands were observed when time-resolved spectroscopy was used: i) a broad.22 indicate that the radiationless deactivation process which accompanies the observed fluorescence is in agreement with Equation 4. 0-150 ps. structureless band with a maximum at 420 nm and a corresponding lifetime of 250 ps and ii) the wellknown band of pyrene excimer.

Fluorescence study on intermolecular complex formation between mesogenic terphenyldiimide moieties of a thermo-tropic liquid-crystalline polyimide. with permission from Elsevier Science) Figure 4. Huang. Volume 40. Huang.W. K. Watanabe. Horie and J. (Reprinted from Polymer.Luminescence Studies of Polymers Figure 4. T. T. copyright 1999. Fluorescence study on intermolecular complex formation between mesogenic terphenyldiimide moieties of a thermotropic liquid-crystalline polyimide.22 Arrhenius-type plot for the change in lifetime of fluorescence of liquidcrystalline polyimide during heating (Reprinted from Polymer. 3826.W. copyright 1999. Kaneko. H.21 Temperature dependence of the fluorescence peak wavelength during heating of thermotropic liquid-crystalline polyimide. Horie and J.I. 3826.I. H. Volume 40. K. Excitation at 320 nm. Kaneko. Watanabe. with permission from Elsevier Science) 135 .

of probe molecules incorporated in the polymer chain can be used to a large extent to study molecular motion. Guillet. London. 2. For example.E. VCH Publishers. J. 1985. Organic Molecular Photophysics. 1973. John Wiley & Sons. principally fluorescence. NY.5 Conclusions Many of the significant features observed in the photophysics and photochemistry of polymer systems have been shown to have their origin in the way the behaviour of electronically excited states are affected by molecular motion. order. or (iii) if the luminescent species is randomly distributed along the polymer chain or not. measurement of the relative intensities yields information concerning the ordering of the polymer chain and similarly studies of the kinetics of fluorescence decay yield information on energy migration and segmental motion. Michl. Cambridge University Press.Handbook of Polymers in Electronics 4. Excited States and Photochemistry of Organic Molecules. The excited state properties.B. 136 . USA. UK. Inc. The present review has revealed how fluorescence methodologies can provide an insight into the nature of the intramolecular and intermolecular interactions.. (ii) if the luminescent species is attached to the polymer or detached from the polymer. Polymer Photophysics and Photochemistry. Acknowledgements This work was supported by KBN grant No. and energy migration in polymeric systems. Most of the phenomena involve a competition between physical processes leading to non radiative deactivation and emission of the excitation energy. and thus are most easily observed in the characteristics of fluorescence. 3 T09B 058 14 (Poland). References 1. New York. J. Which of the parameters is of prime importance depends largely on: (i) the environment of the luminescent species. Klessinger and J. 1995. M. which are responsible for thermally initiated variations as well as the formation of microstructures and the morphology of a polymeric medium. Cambridge. Birks. 3. The competition between processes can be controlled by either thermodynamic or kinetic parameters. The changes in fluorescence intensity and fluorescence lifetime around phase transition temperatures can yield information on packing pattern and variation with thermal treatment of the polymer during the phase transition.

McDonagh. J. Ithaca. The Royal Society of Chemistry. Cambridge. Maunder. 1993. Analytical Chemistry. 2025. 95. McEvoy. 1967. C. C. Lakowicz. 1960. D. 9. 1991. P. 7. Cambridge. J. The Royal Society of Chemistry.S. 14. J. Parker and W. UK.T.D. J. Melhuish. D. 293. Lakowicz and J. Weller. 1. P. Polymer. NY. 32. Volume 1. 1961. Journal of Physical Chemistry.. Th. 16.. B. D. Imhof and S. Wandelt. Beens. 70. Eds. Ed. Birch. 65.A. 1. 1998. J. Nakashima. 12. Kelly. 70. 5.E.de F. Rehm and A. Journal of Physical Chemistry. Neue Folge. New York. 1991. 10702. Kelly.H. 10. McArdle and M.de F.. C. Ledwith in Photochemistry and Polymeric Systems. 47. Winnik. 18. Principles of Polymer Chemistry. 97. 56. Phillips in Photochemistry and Polymeric Systems.B. Analyst. Radhakrishnan in Photochemistry and Polymeric Systems. 68. 15. Plenum Press. Weller. H.S. 1993. B. D. Maunder. Flory.R. UK. 6. B. Volume 1. 1954. Plenum Press. Kasper. Eds. Eds. H. Cornel University Press.B. C. 229. Zeitschrift für Physicalische Chemie.M. Journal of Chemical Physics. Maunder. Knibbe and A. Gryczynski in Topics in Fluorescence Spectroscopy Techniques. Wandelt. C.J. 587. New York. USA. 1953.J.A. Birch and R.D. Wandelt. Ed. 13. 275. B.J. MacCraith and A.S. de F. Zeitschrift für Physicalische Chemie.Luminescence Studies of Polymers 4. 1. Bath.E. Förster and K. Knibbe. Darling and W.A. W. Lakowicz. 1183. Kelly. 1993. 1998.M. UK.R. Rees. 8. K. 87... Turkewitch. J. Imhof in Topics in Fluorescence Spectroscopy Techniques.B. McArdle and M. 2707. 45.M. Analytical Chemistry. 1991. J. 137 . 17. Pethrick.J. 85. Neue Folge. H. NY.K.R. Duhamel and M. G. 11. 1967.J.J. McArdle and M. R. The Royal Society of Chemistry. 1993. Powell. R. A.

12.C. Polymer Physics. 473. Y. 1965. Bulletins of the Chemical Society of Japan. 3163. Journal of the American Chemical Society. 1968. Phillips. Soutar. Okamoto and S. 1970. 218.A. 68. Polymer.W. A. 1101. European Polymer Journal. 8.J. 16. Japan. European Polymer Journal. Journal of Polymer Science. Somersall and J. L.A. C. Macromolecules. 56. 1972. 1987. 1082.E. 1969. 1971. 1979. Guillet. 32. 28. Geuskens. 24. Dempster. David. 369. 1976. K. 25. Radic. 28. 61. Winnik. Journal of Chemical Physics. 1972. S. Chemical Physics Letters. Perico. 1980. Report on Progress in Polymer Physics. 24.D. 34.B. E. 29.E. 2680. Piens and G. 1532. 49. Macromolecules. Roberts and I. B. 8. M. Svirskaya and A. 6. 50. C. Mar. L. Cuniberti and A. 23. A.A. C. 31. 1972. Testa. Lumb. 421. Polymer.A. European Polymer Journal. Journal of Chemical Physics. P. 30. 1526. R. 22. Lissi. Gargallo and D. Redpath. Rusakowicz and A.E.A. Fox. David.H. F. 27. A. Harrah. 1979.Handbook of Polymers in Electronics 19.E. Itaya. 1973. Kubayashi. 36. 2401. 13. North and J. 92. 1019. Journal of Physical Chemistry. 1974. 20. 956. 2. E. A. Journal of the Chemical Society Faraday Transactions I. 18.A.E. Yamamoto. 26. Guillet. A. 374.M. 42. C. 1983. 138 . J. 37. Katayama and M. 12. Szumilewicz. Guillet. 35. 385. Wandelt and J. K. 21. 13. M. C. 1980. Cozzens and R. Mitani. Macromolecules. Soutar. European Polymer Journal. A. 1970.C.C. 2083. Geuskens. 793. R. Journal of Chemical Physics. Aspler and J. Hoyle and J. 1291. 1977. Hirayama. Al-Watter and M. Abuin. Chandross and C. E. 33.J. Frank and L. D. 72. Piens and G. Harrah. 3586. 38. 1972. M.F.J. Nishijima. Journal of Chemical Physics. 1791.

1979. UK. B. Pethrick. 47. Imhof. 31. D. Macromolecules. 575.E. 1953. D. 1982. Bluhm and P. B. D. R. 5141. Journal of the American Chemical Society.S. Hung and H. Keller. 50. 42. 12.M. 40.M. 1984. Polymer. 53.J. N.D. 1982. 54. 55. Macromolecules.R. 924. M. Hill. 104. Kryszewski.A. Imhof.S. 9. Wandelt. Roberts and G. Scaling Concepts in Polymer Physics. P. 1991. Tyrer. Colloid Polymer Science. F. 139 . Winnik. Polymer Bulletin. M. Jachowicz and M. J. 32. 43. 2765. 19. Soutar. 1979.M. Holmes and R. Horwitz and D. Winnik. J. 262. Redpath and M.S. Birch. London. B. T.Luminescence Studies of Polymers 39. A. B. 1981.A. 1986. Pethrick.A. 73. 45.S.J. Kryszewski. 22.E. 649. 1984. Atkins.J. 24. Gupta. Morawetz. 1990. M. 1982.J. 17.M. 24. Sarhene and J. 637.E. Journal of Polymer Science. Gupta. Discussions of the Faraday Society. 1372. North and R.S. 1759.A. Kops. Birch. Wandelt. 1982. 4. Cornell University Press. Acta Polymerica. Polymer. B.C. Polymer Physics. Pethrick. 2296. 1983.O. 13. Imhof. 1959. Kliger. Wandelt. 836. D. 15. Förster. Macromolecules. 51. Kryszewski. Sundararajan.E. 27. A. 44. Birch. Macromolecules. J. R. A.R. Th. Dexter. 49. Shapiro. Jensen and J. A. M. F. D. Amrani.L. E.G. A. 21. 2125. 20. 1981. E. Polymer Chemistry. 56. A. 755.A. Phillips. 23. D. 52. 41. 199. 5604. L. B. 48. de Gennes. North and R. R. Rumbles. 1981. Jarvis. Wandelt. European Polymer Journal. Sundararajan. 22. A.J. Journal of Polymer Science. Polymer Communications. Journal of Chemical Physics. Wandelt. Macromolecules. P.T. J.J. Wandelt. 1980. 46.

17. T. Wright and D. Watanabe. 60. F. B.A.E. 68. Polymer Physics. 1990. S. 3558. 61. Heisel and G. 64. Phillips. 65. M. Nishimura and I. 2782. Y. Itagaki. R. Rumbles and J. Matsunaga.I. 1988.S. Tsunomori. Birch. 40.A. Macromolecules. D. R. Huang. Wandelt.A. Imhof and R. Y. 63. Handa and S. 1978. 1969. 66. 1881. Journal of Physical Chemistry. T. Pethrick. 2782. K. F. 209. 23. 66. W. J. Horie. European Polymer Journal. 1978. G. 1597. 79.W. Pethrick. Hu. Journal of Polymer Science C Symposia. 1992.Y. H. T. A. 67. Macromolecules. Tagawa and Y. Hu.J. 1761. 26. Mita. Lockhead and A. Roberts. Macromolecular Chemistry. S. Tao and C. K. R.S. 1967. 94. 7324. Laustriat. Wandelt. Horie. 11. H.J.J. 35.M. 1981. 16. 1999. 1983. 70. 49. 3552. M. K.C. Imhof and R. Washio.M. North and D. Tsunomori and T. 69. Frank. 140 . 40. 55. H. Yamashita and F.P. 1970. North. Winnik. 1993. 72. A. Soutar. D. Frank. 25. 62. T. G. Tabata. Ishii. I. Discussions of the Faraday Society. R. Macromolecules. Ushiki. K. Horie. 59. K. Journal of Polymer Science. 1992. Kaneko. Y. Polymer. Phillips. 33. Yamashita.W. Polymer. 1976. Macromolecules. Yamazaki. Birch. D. Tamai. Macromolecules.A. Macromolecules.W. 71. 1983. 3821.Handbook of Polymers in Electronics 57. 1992. 33.B. 1960. Dew. Journal of Chemical Physics. 259. R. Ross. F. B. Gashgari and C. 96. N.M. 244.D. Yonezawa. 73. Ghiggino. MacCallum. Natta. 58. Journal of Chimie Physique. 21. 1499. Horie and J. 16. Ushiki. H. 1992.E. 3996. Polymer. J.

but where the electronic properties of conjugated macromolecules can be tailored for specific applications. the development of polymers for electronics is still an open field where polymers are used not only as insulators. In the following years. the great interest in polymers was due to the good mechanical properties associated with materials having low density and low processability costs. The light emitting diode (LED) was formed by a single layer of PPV sandwiched between an indium tin oxide (ITO)-coated glass and an aluminium cathode which was vacuum evaporated on the top of the polymer film. After this discovery. which is a young branch of chemistry. while holes are injected at the anode. In particular. many polymeric structures were synthesised with the aim of improving both the electrical conductivity and the stability of the materials. Different strategies were developed. Later the possibility of combining new chemical functions in a backbone opened new fields of applications for macromolecules.05%. work by Tang and Van Slyke [2] on the electroluminescence (EL) of aluminium 8hydroxyquinoline (Alq3) stimulated a great amount of work worldwide on the generation of light by electrical excitation in organic materials. has been the subject of great development both as a basic and applied science in the last 30 years. In the first instance. the number of scientific contributions on polymeric LEDs increased consistently. at the beginning.2 eV with an external quantum efficiency of 0. all addressed to understanding the basic mechanism of the injection of opposite charges in the polymers. The problem which confined the use of polymers only in the area of insulators was overcome in 1977 with the discovery by McDiarmid and Shirakawa [1] that iodinedoped polyacetylene possesses metallic conductivity. Botta 5. So structures with specific uses were developed creating new interfaces with technological fields that. Bolognesi and C. biology. and their radiative recombination. were unusual for polymers: pharmacology.1 Introduction Polymer science.5 Polymers for Light Emitting Diodes A. optics. their travelling in the thickness of the layer. electronics. Injection of electrons takes place at the cathode. It was in 1990 that Friend and coworkers [3] presented the first electroluminescent polymeric device able to emit at 2. medicine. all these factors being fundamental for the increase of efficiency and lifetime. 141 . At the end of the 1980s.

Handbook of Polymers in Electronics The great effort that is still pursued in this field is responsible for both the optimisation of new polymeric structures and for the preparation of new and more reliable devices.5 eV range. which are symmetrically displaced from the midgap. the closer the levels to the midgap. describes the properties of the polymeric semiconductors by introducing a strong electron-phonon interaction. Seiko-Epson and Cambridge Displays Technology are developing a technology using ink-jet printing of electroluminescent material for colour patterning. The more extended the defect.2 The Physics of Electroluminescent Devices 5. obtained via charge injection from the electrodes. According to this theory. The development in this area is extremely fast. respectively. a few aspects of this very wide field are summarised. The optical transitions occurring between these levels and the conduction and 142 . often referred to as SSH. It has been recently reported that Philips will be able to produce backlighting and segmented displays very soon [4]. The Su. due to the Peierls instability. through an electrode or by photoinduced interchain electron-hole (e-h) separation) leads to the formation of singly charged polarons or doubly charged bipolarons. 5. for non degenerate ground state polymers. developing LED prototypes.5-3. This produces two localised electronic states within the forbidden energy gap. 13].1 The Physics of Conjugated Polymers Several reviews have been reported on the electronic properties of conjugated polymers [69] as well as on the physical mechanisms occurring in LED devices [10-12]. Both the charged and the neutral excitations are stabilised through a local modification of the bond alternation. Conjugated polymers possess strongly anisotropic electrical and optical properties since the π-electron delocalisation occurs along the chain direction. [6. Schrieffer and Heeger theory. depends on the spatial extent of the defect (polaron or bipolaron) [14]. focusing on the properties of the electronic excitations which are more relevant in the physics of an electroluminescent device. An ideal conjugated polymer chain possesses a one-dimensional structure which. The energy position of these levels. The fast development of this branch of polymer science has stimulated the interest of the industrial world and nowadays there are several small. in reference [5] some of the web sites continuously updating in this field are reported. both in the chemistry area and in the microelectronics sector. Neutral species (exciton-polarons) can be generated by photoexcitation via e-h separation or by the fusion of two polarons with opposite charges. and are responsible for photoluminescence (PL) and EL.2. injection of charges (by chemical doping. Here. leads to the electronic structure of a monodimensional semiconductor with an energy gap typically in the 1. It is suggested that the reader visit these sites for the very latest news. medium and big enterprises. where electron-electron (e-e) interactions are neglected.

20]. there are several areas of the physics of conjugated polymers which cannot be explained without taking into account the e-e interaction effects.Polymers for Light Emitting Diodes Figure 5. expressed by the PL quantum efficiency. When the exciton is created by the coalescence of two polarons. by photoinduced absorption. are created by photon absorption (direct triplet generation is forbidden from the spin selection) and recombine radiatively with a certain probability. the PL is due to the spin-allowed transition from the upper to the lower of the polaron-exciton levels. According to this model. Only singlet excitons. and by charge injection. the coulombically bound eh couple can be described as a Frenkel exciton (localised within a molecule) or a Wannier exciton (extended over many molecular units). Indeed. models generally applied to the physics of molecular organic crystals [15] are more appropriate. the probability of forming a singlet exciton is 1/4 while 143 . When interchain interactions are strong.1) account for the sub-gap optical absorption bands observed by chemical doping. In conjugated polymeric systems. charge transfer excitons are formed.1 Scheme of the generation and radiative recombination of the singlet exciton S by photoexcitation (a). 19. as excimers and exciplexes [15. ηPL (the ratio between the number of photons emitted and the number of photons absorbed). according to its binding energy or degree of localisation [16-18]. S. measured with photoinduced absorption techniques. the PL emission is generally observed at energies higher than the spacing of the two polaronic levels. and by charge injection (b) mechanisms valence bands (see Figure 5. In order to describe the phenomena related to the neutral excited states of conjugated polymers (which are primarly involved in the physics of LEDs). However.

By applying a bias voltage at the electrodes. The degree of order and crystallinity of the material plays an important role in these processes as well as in determining the charge mobilities [28. 22].2 The Physics of the Device In this section.2 Scheme of a single layer LED The working mechanism of the device is shown schematically in Figure 5. The position of the HOMO and 144 . some basic information on operative guidelines is provided for readers who are new to this field. A glass substrate coated by ITO is used as a transparent (positive) electrode. 5. If only one polymer is used. Figure 5. by a proper selection of the materials. light emission is obtained through the transparent electrode. The typical structure of a single-layer polymeric LED is shown in Figure 5. exciton migration effects decrease the ηPL of the material since the probability of exciton quenching by impurities is increased.2. A polymer layer is deposited onto the substrate by a spin coating technique. 29]. a metallic layer which forms the negative electrode. where the levels of the electrodes and the HOMO (highest occupied molecular orbital) and LUMO (lowest unoccupied molecular orbital) of the polymers are reported. On top of the polymer is deposited.Handbook of Polymers in Electronics for a triplet exciton (which does not contribute to the EL emission) it is 3/4 [21.3. the exciton migration processes may red shift the emission and also increase the emission efficiency [25-27]. together with the intragap levels of the polarons and the exciton-polaron. If more than one material is used (blends or heterostructures).2. LEDs are devices that transform electrical signals into optical signals. After an exciton has been created. it moves in the material by hopping or by resonant transfer processes [15. by vacuum evaporation. 23-26].

IP is the ionisation potential. The working mechanism of a LED consists of four main steps: (1) By applying a bias voltage. The efficiency of an EL device (ηEL) is the ratio between the number of the emitted photons and the number of injected charges. LUMO of the polymer. are determined by the ionisation potential (IP). S. the electronic affinity (EA) of the polymer and the workfunction (φ) of the metals. φ is the metal work function. HOMO is the highest occupied molecular orbital. driven by the applied electric field. relative to the Fermi levels of the electrode.Polymers for Light Emitting Diodes Figure 5. (4) S recombine radiatively by photon emission. 145 . as shown in Figure 5. Δe and Δh are potential barriers for negative and positive charges.are positive and negative polarons. LUMO is the lowest unoccupied molecular orbital.3 Working mechanism of a LED: P+ and P. (3) Polarons of opposite sign couple to generate the excitons.3. (2) The charges P+ (P-) move in the material towards the negative (positive) electrode. charges of opposite signs are injected in the active material and form positive and negative polarons.1) where γ is a factor dependent on the double charge injection (γ = 1 for perfect charge balance). EA is the electronic affinity. ηEX is the efficiency of singlet exciton generation (maximum ηEX is 1/4) and ηPL is the measurable PL quantum efficiency [30]. It can be expressed as ηEL = γ ηEX ηPL (5.

the introduction of a conducting polymer interfacial layer between the ITO and the active polymer has been reported to provide φ determined by the intermediate polymer [37]. The efficiency of radiative recombination of the S exciton is directly related to ηPL. 41]. iii) Exciton generation.Handbook of Polymers in Electronics Some considerations can be made on each of the four steps in order to increase the device performances: (i) Charge injection. aluminium (4. The introduction of an ETL also has the advantage of reducing the hole currents. The efficiency of exciton generation can be optimised by increasing the probability of polaron coalescence. and can be maximised by reducing the quenching centres and by localising the exciton (polymer blends. 43]). PANI [31. The high trapping of negative charges is responsible for bias-dependent efficiencies with low efficiency near the onset voltage.are easily trapped. copper and several alloys are used [38]. Factors which limit the radiative recombination are an excess of density of charges (exciton-polaron quenching) and quenching by the electric field [47-49]. with φ in the 4. silver. Improvement of charge transport can be obtained by inserting an electron transporter layer (ETL) and a hole transporter layer (HTL) between the active material and the electrodes. conjugated polymers are better hole than electron transporters. as it acts as a hole blocking layer. The active area of the polymer must be far from the electrodes. thus increasing the charge balance [40. where a high concentration of quenching defects are present [44-46]. calcium (2. These effects can be reduced by improving the charge balance and by reducing the working bias voltage (V). This is generally obtained by confining the active layer at the interface between two materials (heterostructures). since P. This is obtained if the electrode metals have φ such that the potential barriers for positive (Δh) and negative (Δe) charge injection are similar (Δe≈Δh). which controls the injection of the minority carriers [33. These processes also red shift the emission.9 eV). conjugated copolymers.3 eV). The number of injected positive and negative charges must be similar. (ii) Charge transport. Calcium usually gives the best results since the device efficiency can be increased by reducing Δe. For the negative electrode. conjugatednon conjugated copolymers [42. 34.5-4. Unfortunately. indium. A good balance of positive and negative charge transport is necessary. Another way to increase the radiative recombination probability is to transfer the excitation from one material to another (more efficient) material (lower gap polymer or dye) by resonant energy processes such as Foerster transfer. Recently. (iv) Radiative recombination.2-4. 39].8 eV range [33-36]. Positive electrodes generally used are ITO. through a good balance of positive/ negative charges in a restricted active volume (heterostructures) [40]. 146 . 32] and silver.

4 Typical I-V and EL-V curves for a single layer LED based on poly(3-alkylthiophene).Polymers for Light Emitting Diodes 5.2. If the current onset is at lower voltages than the EL (as in the case of Figure 5. through their ratio. 47. The spectral shape of the EL is then compared with the PL of the active material. the two curves are similar and possess the same onset voltage. as well as internal electric field distribution analysis. while emission influenced by chemical degradation of the polymer [44] or by interference effects [45] is often observed when the emitting material lies at the polymer-electrode interface. the I-V (current intensity versus bias voltage) characteristic together with the EL-V (EL intensity versus bias voltage) curves are measured. The studies on fluorescence quenching induced by electric fields.3 LED Characterisation In order to characterise a device. and. 147 .4). In Figure 5. Von. the external efficiency of the device is deduced taking into account the geometrical factors [50]. 21. The same spectral shape is expected when the active region is in the bulk of the material. The onset voltage (Von) is shown. have provided deep insight into these phenomena [16. Figure 5. Many LEDs have been studied in order to gain information on the detailed physical mechanisms involved in their operation.4 a typical behaviour of a LED is reported. When a good charge balance is obtained in the device. an excess of positive charges is usually responsible for biasdependent efficiencies. 51-59].

step growth polymerisation. 5. For example. Several synthetic routes have been reported for the preparation of this polymer. but there is still a lot of work to do because improvements both in lifetime and in electroemission efficiencies are possible. but the great efforts provided by many groups in this area have lead to exciting results for both improvements in macromolecular chemistry and in technological application. because when the growing chain is formed by 6-10 repeating units.3 Polymeric Structures for LED The tailoring of polymeric structures plays a significant role in the development of this new technology. a soluble form of a precursor was synthesised. a subsequent thermal treatment of the film lead to the insoluble conjugated thin film of PPV.Handbook of Polymers in Electronics 5. and this is related to the PL and EL efficiency [33. for its good PL and EL efficiencies. A thin film of the precursor was formed by spin coating techniques. The role of many factors are almost completely understood. it becomes insoluble and chain growth stops. 34]. To overcome these difficulties. Optimisation of all the above parameters is extremely difficult on a chemical synthesis basis.5) was one of the first polymers studied.3. Its insolubility is a great problem in the preparation of high molecular weight materials.1.1 Polyphenylenes 5. and Resistance to oxidation and to temperature of the active polymeric layer are fundamental to the lifetime of the device. The solid state packing of the macromolecules influences the stability and the emission efficiencies [42].3. The surface polarity of the polymer is responsible for the adhesion between the active polymer and the electrodes.1 PPV PPV (Figure 5. such as Wittig condensation between terephthaldicarboxaldehydes and arylene-bisphosphylidenes gives very low molecular weight polymers. Polymer chemists have synthesised from the beginning new structures in order to obtain the desired properties of conjugated macromolecules. 148 . The EA and the IP of the polymer strongly affect the charge injections from the electrodes into the polymers. The structural control can be extended to several physicochemical parameters: • • • • • The band gap of a conjugated polymer is responsible for the PL and EL peak position. The low molecular weight polymers synthesised in this way cannot be used for thin film preparation because they are insoluble. which is an important factor in charge injection.

D.R. introduced by Gilch [68] in 1966. Friend. Dialysis.5 Structure of PPV The Wessling method.H. 261-264. Several modifications of this general procedure have been introduced.+ + Cl(II) X = S(CH3)2 n PPV 200 °C. Another procedure. -OH (0. A. R.C.B. N2 2. to pH = 5-7 3. 3 days (dist. 41-43. Studies of the Efficient Synthesis of PPV and Dimethoxy-PPV. H2O). 0°C. Holmes. 1h. with permission from Elsevier Science) 149 . Bradley. r. XH2C (0.4 M / H2O).6 Synthetic procedure for PPV (Reprinted from Synthetic Materials. Brown.L. consists of the polymerisation of dichloro-p-xylene with potassium tert-butoxide in organic solvents.+ or + ClX = S(CH3)2 1. 1 h vacuum (I) X = S Cl. P. N2 H 2C CH2 X n 300 °C. H+ (0. was one of the first reported [60].Polymers for Light Emitting Diodes n Figure 5.4 M / H2O). consisting of changing the conditions of the transformation process [62-64] and/or the nature of the chemical species to be eliminated [65-67].4 M / MeOH) CH2X X= S Cl. Burn. D. In Figure 5. consisting of the preparation of a sulfonium precursor polymer.t. 2 h n HCl (g) Solution in MeOH H 2C (III) CH OMe Solution in CHCl3 Figure 5. A.6 the procedure followed to prepare PPV according to [61] is reported. 1991..

e. mainly decaying non radiatively [86]. which are much more relevant in the solid state than in solution. The external efficiency of the simple LED formed by ITO. 150 .05% [3]. 4a. increase both exciton migrations to quenching sites [42. In fact. references are reported for each structure [70-85]. Some of the general criteria followed to prepare these materials are discussed. This is the case of structures 1a. The first EL from PPV stimulated the work of chemists to develop new alternative routes to improve the preparation of this polymer. exhibiting an emission centred at 525 nm that corresponds to yellow-green light. PPV. 1b. highly packed in three dimensions) have the tendency to decrease the PL and consequently the EL efficiency. 43] and the formation of low energy excited states. The idea of having a polymer soluble in organic solvent already in its conjugated form led to the introduction of solubilising groups in the PPV backbone.. strong interchain interactions. 2a. 2b. 4b in Table 5. The use of a calcium electrode increases the efficiencies. This value increases by one order of magnitude if calcium is used instead of aluminium [69]. Highly ordered structures (i.1. it must be noted that polymer PL efficiencies can be very high in solution. rather than linear residues. and aluminium (usually reported as ITO/PPV/ Al).Handbook of Polymers in Electronics Figure 5. but generally decrease by one order of magnitude in the solid state. The introduction of branched side chains. Some of the most studied structures that were developed are reported in Table 5. was found to be effective in lowering the degree of order of the material. was 0.7 Electroluminescence spectrum of PPV The EL spectrum of a LED prepared with PPV is reported in Figure 5. For example.7. but this metal is very reactive to humidity and its use may be allowed only in an inert atmosphere or when the electrode is well covered with a protecting layer. Consequently.1. A detailed description of the synthesis for their preparation is not given. preventing the tight packing of the macromolecules.

in the same structure. It is worthwhile mentioning that in [70] a simple flexible device of PANI-polyethylene terephthalate (PET) is described. Some of the materials are block copolymeric structures (9. where the MEH-PPV active layer is directly formed onto a thin aluminium wire. According to these findings. An example of a needle-like LED is described in [88]. a blend film is obtained. while in other structures. The drawbacks of blending mainly consist of the higher working voltage and a decreased lifetime of the devices [89]. in different ratios. 12 and 16). resulting in the formation of an almost amorphous PPV with an EL efficiency of 0. blending allows a decrease of the interchain interactions. although a repeating unit can be identified. on the top of the PANI layer a film of MEH-PPV (poly[2-(2´-ethylhexyloxy)-5-methoxy-1. the combination of different monomeric units. The advantage of this LED with respect to other ones (where glass is covered by ITO) is that PET and PANI are flexible. As in the previous table. by spin coating the mixed solution. 151 . The cathode is then formed by deposition onto the active layer of a thin transparent film of PANI thus obtaining an electroluminescent wire. Soluble electroluminescent polymers can be dissolved with non electroluminescent polymers. 91-101]. In fact. the mixing of two different polymeric materials often leads to phase segregation which has to be avoided if a decrease in the interchain interactions is required. This is a reliable method for improving the efficiencies both in PL and EL. The electron injecting electrode was formed by calcium. PANI is a soluble conducting polymer which acts as a hole injecting electrode substituting ITO. resulting in a change in colour emission. Changing substituents also has the effect of modulating the gap. In Table 5. for each structure references are reported [69. a simple ITO/MEH-PPV (1a)/Ca LED was reported to give an external quantum efficiency of 1% at 620 nm [70].22% for a simple ITO/PPV/Al LED. This example shows the potential of polymeric materials with respect to inorganic compounds which cannot give large flexible electroluminescent areas. Moreover. the copolymeric approach is a suitable method for further tailoring the electrooptical properties of the active layer. The synthesis of conjugated copolymers is another approach followed to prepare new structures useful for device preparation.Polymers for Light Emitting Diodes Son and co-workers [87] found that the introduction of cis double bonds in a PPV interrupts the conjugation and disturbs the polymer chain packing. the term copolymer is preferred because more than one chemical function appears in the repeating unit.4-phenylenevinylene]) was deposited. Moreover. In fact.1.2 some of the many soluble copolymers based on the PPV structure are reported as examples. the glass transitions have to be taken into account for the preparation of devices where the dimensional stability is very important. The structures so far prepared are mainly amorphous. as shown in Table 5. allows a fine modulation of the properties of the materials [90]. hence the device can be completely bent without failure. The preparation of a suitable film by spin coating or by casting from solution is the key step for development of new interesting devices.

For some structures the external and/or internal efficiencies are reported together with the kind of cathode used and wavelength of the EL emission OR (a) MEH-PPV n R= OCH3 Elmax = 620 nm. ηel = 1% (Ca cathode) [70. 72. 76] R= (c) [77] R= 1 OR (a) n R= OR Elmax = 560 [78] (b) R= Elmax = 560 2 [79] 152 . 71.Handbook of Polymers in Electronics Table 5. 73] (b) OC1C10 [74. 75.1 PPV derivatives used as active materials in LED.

1 Continued OR CH3 (a) n R= Si CH3 C6H12 OR R' = [80] CH3 (b) R= Si CH3 Elmax = 540 nm. ηel = 0. 8.05% (Al cathode).Polymers for Light Emitting Diodes Table 5.1% (Mg cathode).0003% (Al cathode) [81] CH3 (c) R= Si CH3 Elmax = 564 nm. ηel = 0. 10 [83] R' R' = –(CH2)nH (b) R= Elmax = 510 nm.08% (Ca cathode) [82] R R (a) n R= n = 6. [84] 4 0. C8H18 R' = H CH3 R' = H 3 0.002% (Al cathode) 153 . ηel = 0.

01% (Al cathode) [85] Table 5. Al cathode) [91] 7 OC6H13 OC6H13 CN C6H13O NC C6H13O n Elmax = 710 nm. 93] 154 .Handbook of Polymers in Electronics Table 5. 0. ηel = 0. ηel = 0. both Ca and Al cathode) [92.2% (internal. Ca cathode).1 Continued 5 Z (a) (b) Z=H R= Z = SO2CH3 n OR Elmax = 540-560 nm. ηel = 0.07% (internal.2 Examples of complex polymeric structures used as active materials in LED 6 S C12H25 OC6H13 CN n CN OC6H13 Elmax = 750 nm.2% (internal.

2 Continued 8 C10H21 C10H21 N N N Elmax = 540 nm. ηel = 0.3% (Al cathode) [69] 10 OCH3 OC7H15 OCH3 OC7H15 n Elmax = 590 nm [95] 11 R OCH3 O(CH2)6 R OCH3 OCH3 O n OCH3 Elmax = 455 nm [96] 155 .Polymers for Light Emitting Diodes Table 5.02-0.015% (Al cathode) [94] 9 OCH3 n m OCH3 ηel = 0.

02% (internal.2 Continued 12 C8H17 Si O * n OCH3 m Elmax = 576-618 nm. ηel = 0.1-0.Handbook of Polymers in Electronics Table 5. Al cathode) [97] 13 n [98] 14 R Si R [99] n 15 n CN N [100] 156 .

2 Continued 16 OC10H21 OC10H21 OC10H21 * OC10H21 * n * m p Elmax = 515-567 nm [101] Structure modulation. interrupts the conjugation path giving emission peaked at around 450 nm. through a proper choice of the monomeric units forming the copolymer. the increase of the electron affinity through the introduction of suitable electron withdrawing substituents has been found to be very promising. altering the copolymer composition allows tuning of the band gap. peaked at 850 nm) of copolymer 6 in Table 5.2% were reached both with a calcium and aluminium cathode in a single layer device [92]. are lowered.. One of the factors that induces a decrease in the EL efficiency is the poor suitability of polymers to transport one of the injected charges. due to the presence of cyano groups. A suitable chemical approach to increase the injection of electrons consists of increasing the electron affinity of the polymer for the minority charge carriers. As most of the semiconducting polymers are easily p-doped and not n-doped. resulting in an imbalance in the recombination.2-(4-(p-ethylphenyl))triazole (TRIDSB) [94] (structure 8). i. internal quantum efficiencies up to 0. the control of the emission colour extending from the red.2) showing emission at 710 nm. The insertion of a non conjugated segment or of a silicon atom. However. has a great influence on its electronic properties. so that good injection of electrons both from calcium and aluminium occurs and equivalent efficiencies are obtained even though the two metals have different work functions. for PPV single-layer devices. the lowest unoccupied orbitals.e. respectively.13)-didecyl)distyrylbenzene-co-1.20-(10.Table 5. to the orange/red of the cyano-PPV [92] (structure 7) or of its derivatives [93] and to the blue of poly(1. it was reported [69] that the quantum efficiency with the calcium electrode is one order of magnitude higher than the corresponding device where aluminium is used.2 [91]. forming the conduction band. It is important to remark that. near IR region (700-1100 nm. This is the case of structure 7 (Table 5. 157 . Another example of modulation of the gap is shown in copolymers 11 and 14.

other electron-deficient nitrogen containing groups such as oxadiazole [102. The EL spectra are almost equivalent for a simple ITO/10/Al configuration. The cyano-PPV approach was extremely useful and other withdrawing substituents were introduced in the PPV backbone with the aim of increasing the electron affinity. The number of low molecular weight molecules synthesised as hole or electron transporters is extremely high.3. 105] and quinoxaline [106] were also introduced in the polymer structure. pyridine [104. and also with alternate field.8 Hole transporter (tetraphenyl diaminobiphenyl (TPD)) and electron transporter (2-(4-biphenyl)-5-(tert-butylphenyl-1. Good electron transporting molecules include 1.8) are good hole transporters.Handbook of Polymers in Electronics An even better balance in the injection of the opposite charges was found when another layer more suitable for hole transport.3. As previously reported.8. is used [70].4-oxadiazole (PBD)) 158 . formed by ITO/PPV/cyano-PPV/Al has an internal quantum efficiency as high as 4% with emission at 610 nm [70]. Two of the simplest molecules are shown in Figure 5. triazole [94].e.4-oxadiazole on the top of the polymeric emitting layer. the balance between the two opposite injected charges is one of the main goals of this area. Apart from the increase in the electron affinity of the material. the adding. N N TPD CH3 H3C CH3 O PBD N N Figure 5. A doublelayer LED. Figure 5. while triphenylamine and related structures (TPD.4-oxadiazole derivatives. such as unsubstituted PPV.3.. in the proper position (i. 103]. near the cathode or near the anode) of an additional layer formed by polymeric material and/or small molecules as electron transporters or hole transporters was found to be very useful. An example has already been reported above: PPV has been used as a hole transporter in a double-layer configuration LED [92]. Copolymer 10 was found to give bright EL either with a dc forward bias or with a reverse bias voltage. A simple method to obtain a better electron injection consists of the deposition of a layer of 1.

Polymers for Light Emitting Diodes It was found.4-ethylenedioxythiophene) (PEDOT) and polystyrene sulfonated acid (PSSA) 159 .4. PSSA. polymeric hole or electron transporters have also been prepared [111.9 Poly(3. Nüesch and Yang [114-116] followed similar approaches to control the performance of a MEH-PPV based device and a polyparaphenylene-based device respectively.4-ethylenedioxythiophene) (PEDOT). n O O S PEDOT n SO3H PSSA Figure 5. There are examples in the literature where the balance between holes and electrons is reached by inserting a hole blocking material between the ITO and the active polymers. that devices having 1. Incorporating hole or electron transporting molecules in the polymer backbone is a general procedure that has also been applied to other emitting polymers [108-110].-oxadiazole derivatives. as electron transporters in the form of a vacuum evaporated thin film. or other low molecular weight molecules. mixed with polystyrene sulfonated acid. 119] reported that poly(3. Other materials were found to be very efficient if introduced between the ITO and the active layer. Greenham. PANI was reported to improve the performance of a PPV LED [116]. Very recently this subject has been studied by means of the ultraviolet photoelectron spectroscopy (UPS) technique [37]. For example.9) has a meaningful effect both on the lifetime and in the EL efficiency if spin coated between ITO and the active polymeric layer. have a short lifetime.3. 112]. Many authors [118. a feature probably associated with recrystallisation or aggregation phenomena [107]. (Figure 5. The high interface area between the PANI film and the active luminescent layer enhances the local electric field increasing charge carrier injection [117]. however. a simple polymethylmethacrylate (PMMA) monolayer prepared by means of the Langmuir Blodgett technique was reported to give a four-fold efficiency increase if introduced between the ITO and the active layer [113].

So. is not planar. 5.3. even though one of the first LEDs emitting in the blue region was prepared from conversion of unsaturated PPP [121]. the polyparaphenylene (PPP) structures were intensively investigated with the aim of obtaining more robust materials. n n (a) (b) Figure 5. PPP emissions can reach the blue region of the spectrum. Degradation of the polymer near to the surface occurs and this is one of the limiting factors reducing the lifetime of the devices. linear or branched. As the double bonds in PPV are reactive chemical functions which can be oxidised.10 Polyparaphenylene (PPP) (a) and substituted polyparaphenylene (b) PPP. PPP (Figure 5. the band gap is relatively high and emission is shifted towards a higher energy with respect to PPV.10a) is insoluble and only the introduction of alkyl side chains (Figure 5. while the emission of PPV is mostly centered in the yellow-green region.1. 160 .2 Other Polyphenylene Derivatives The deep and detailed work performed by different groups on the many PPV derivatives is only a part of the huge amount of other structures which were investigated with the aim of reaching valuable performances of polymeric LEDs. obtaining thin homogeneous films suitable for LED applications.Handbook of Polymers in Electronics The problem of the interfaces between the conjugated systems and the electrodes has been deeply studied. has enabled the polymers to be solubilised. substituted or unsubstituted. indicating that chemical reactions limiting the charge injections occur at the interfaces [120].10b).

11 An example of an L-PPP An interesting result in preparing devices with red-green-blue (RGB) emission was shown by Leising and co-workers [130] using parahexaphenyl (PHP) as an active emitting layer. The blue emission of PHP was converted by means of a suitable dye layer absorbing in the blue region into green light which excited another dye layer absorbing green and emitting red. with emission in the 460 nm region and internal quantum efficiencies from 2% to 4% [126]. With the introduction of alkoxy-branched side chains. R H C6H13 n C6H13 C6H13 R H Figure 5. The Mullen and Scherf approach [127.12. This shift was also attributed to the formation of excimers due to interchain interactions in a highly planarised. It was also reported that a certain modulation in the emitted light through the applied field variation was possible in the blue-green range [129]. gives high molecular weight compared to previously reported soluble PPP synthesis [123] and an LED prepared with an alkoxy PPP with a two-layer configuration. orientation of the macromolecule axis in the dipping direction occurs.Polymers for Light Emitting Diodes Soluble PPP obtained through the Suzuki coupling. conjugated segment [128]. LEDs having these oriented layers as the active film give polarised EL with a polarisation ratio between the two perpendicular directions of about 5 and an external emission efficiency value of 0. During the transfer process. a remarkable shift towards higher wavelengths was observed for both PL and EL that reached a value of 600-620 nm at the maximum of the peak. 161 .05%. it was possible to prepare the active thin layer by means of the Langmuir Blodgett technique [125]. The introduction of suitable substituents has led to an L-PPP [129] having bluegreen emission with external EL efficiencies of 4% in a single-layer configuration with aluminium as the cathode. as reported by Schlüter and Wegner [122]. An example of an L-PPP is reported in Figure 5. 128] to ladder PPP (L-PPP) provided a good structural improvement for the preparation of stable and tuneable light emitting polymers. As the introduction of the bridges between adjacent monomers induces planarisation of the backbone.11. The light was also spectrally purified with a suitable dielectric mirror/filter. as from [130]. A representation of the RGB LED architecture is reported in Figure 5. A block of substituted phenyl sequences connected with double bonds has allowed for the preparation of copolymer structures that can be used as a thin active layer in an LED. ITO/ PVCZ/alkoxy PPP/Ca reaches a quite respectable EL efficiency of up to 3% [124].

13 the structure of poly(9. 1. 35.3 Poly(phenylene ethynylenes) The desire of polymer chemists to test new structures in the family of phenylenes has led to the preparation of polymers having triple bonds in between two phenyl rings. In Figure 5. These polymers were recently studied for their liquid crystalline behaviour [133] and for the possibility to be oriented and give polarised EL [134. 9. poly(phenylene ethynylenes). 5.3. Alternate copolymers containing thiophene units [132] having PL efficiencies up to 38% in CHCl3 solution at 460 nm were also described. 162 . 135]. 137]. 1997) 5.12 RGB LED architecture [130] (Reproduced with permission from Advanced Materials.9-dihexylfluorene) is shown as an example of this class of polymers [136.Handbook of Polymers in Electronics Figure 5. alkyl side chains of different chemical nature and branching level without seriously affecting the electronic properties of the backbone is one of the advantages of this polymeric family [138].1. as in the case of substituted PPV. 1997. have been prepared and studied for their electrooptical properties.1. PL emissions in the 550-600 nm region were found [131] in polymeric structures having an average degree of polymerisation between 23 and 28. The possibility of introducing. published by Wiley-VCH.3.4 Polyfluorenes Another class of semiconducting polymers containing the phenylene ring has recently attracted the attention of many researchers for its promising properties. alkoxy or alkyl substituted.

This low EL efficiency.000 [139].000 were obtained with a Ni(0) polymerisation. almost unexpected on the basis of the PL quantum yield. This doping is responsible for a more efficient injecting contact at the interfaces between cathode/anode and the active layer. By adding polyethylene oxide in the matrix. giving polymers with molecular weight of 215. the device gave a white emission [142].7-diyl] (BDOH-PF) had a PL efficiency in solution of 77%. was attributed to the poor electron injection. obtained by polymerising the 2.9-di(ethylhexyl)fluorene (PDF2/6) (Figure 5. Soluble polyfluorenes were found to give a liquid crystalline behaviour. For example.7-dibromo-9. Introduction of different amounts of anthracene units in poly(di-nhexylfluorene) did not have a meaningful improvement in the device performance [144]. The introduction in the active polymeric layer of lithium triflate [139].6-dioxaheptyl)-fluorene-2. in a given ratio with respect to the polymer. The corresponding polymer. ITO/BDOH-PF/Ca has an external quantum efficiency of 0. which remains almost constant (73%) in the solid state.3%.7 dibromoderivatives of the monomer by Ni(0) catalyst. Other synthetic approaches through the Suzuki coupling gave lower molecular weight [140]. Pei and Yang introduced 2-methoxyethoxyethane in the 9 position of a fluorene monomer [139]. poly[9. The polar nature of the side chains solvates the ions of lithium triflate that were introduced in the polymer and promote their transport. Addition of inorganic salts. with two sharp peaks in the blue region and a broad intense peak in the green region attributed to interchain excimer emission. upon applying the field. Copolymers having molecular weight ranging from 24. A simple single-layer LED. while external EL efficiencies were around 0. The copolymerisation of fluorene units with other phenylene monomers was studied by Miller and co-workers [143].13 Poly(9.6-dioxaheptyl)fluorene with Ni(0) catalyst is reported to be efficient. High PL efficiencies in solution and the solid state were found for these copolymers. as described by Pei and co-workers [141. 142] induces.14) was found to have a transition into a birefringent fluid phase [145] which can be obtained in a highly oriented arrangement by 163 . poly(9.000 up to 204.9-bis(3. increased the EL up to an external quantum efficiency of 4% in the blue-green region.9-bis(3.15% at 525 nm when tetraethyl ammonium tetrafluorate was added (2%) in the active layer.Polymers for Light Emitting Diodes H13C6 C6H13 n Figure 5.9-dihexylfluorene) Polymerisation of 2. a migration of the cations and anions in opposite directions causing ndoping at the cathode and p-doping at the anode.

the colour emission could be varied by a proper applied voltage [148] from orange to blue (Figure 5. The degree of orientation which can be reached [145] seems to be dependent on the kind of side chain. for example.17). bulky substituents [146] in the 3 position of the thiophene ring or 3.4-disubstituted thiophene and 3-alkyithiophene in different ratios [147].9-di(ethylhexyl)fluorene) – PDF2/6 deposition onto a highly preoriented polyimide substrate [145]. With this simple method it was easy. Tuning of the EL was also obtained by preparing copolymers of 3-alkylthiophene and unsubstituted thiophenes in different molar ratios [149]. Polythiophene derivatives have also been the subject of many studies for their interesting electrooptical properties.3. the so called trans conformation (Figure 5. Berggren [148] used a series of polymeric structures to prepare LEDs covering all the visible range (Figure 5. but only when its soluble form was obtained by introduction of alkyl side chains. 164 .16). the introduction of head-to-head connections leads to a distortion from the planarity of the conjugated system. By blending the different copolymers in a matrix such as PMMA. Poly(3-alkylthiophenes) (PATs) in a head-to-tail configuration are almost planar. Polythiophene was one of the first conducting polymers to be studied. The chance to prepare thin film by solution casting or by spin coating drastically increased the interest in these organic semiconductors. 5. to obtain copolymers with different absorptions from 320 nm to 450 nm.4-dialkyl substituted thiophene [147] inserted in a regular head-to-tail connection have the same effect.14 Structure of poly(9. However.2 Polythiophenes The wide field of research in the area of electroluminescent polymers is not limited to phenyl-like structures. by copolymerising 3. (which acts as an energy transfer blocking material). From the very beginning it was clear that the modulation of the band gap was easy through a proper choice of the substituents. (linear or branched) or on the different packing reached by changing the side chains.Handbook of Polymers in Electronics n Figure 5.15) minimises the steric hindrance between adjacent monomer units.

15 Structure of a trans conformation of a regioregular poly(3-alkylthiophene) S S S IV. 372. 444. Nature. PCHT n n S I. PTOPT Figure 5. PCHMT n S III. POPT n II.Polymers for Light Emitting Diodes R S S R S R R Figure 5. 1994. Inganäs.16 Polymeric and copolymeric structures emitting from 450 nm to 800 nm (Reproduced with permission from O. published by MacMillan) 165 .

446. influences the relative position of singlet and triplet states. which is responsible for a reduced planarity in the backbone.17 Electroluminescence at two different applied field of a blend of different PAT structures (Reproduced with permission from O. 154]. The anisotropy (the ratio of the intensity of the emitted light parallel versus the intensity of the emitted light perpendicular to the drawing direction) was up to 3. The higher EL in PDABT was attributed to the head-to-head connection between two 3-alkylthiophones forming exciton traps thereby hindering their migration to quenching sites [155]. 166 . published by MacMillan) Polarised luminescence was obtained with a simple stretched film of poly(3-(4octylphenyl)thiophene) as an active film.1 [150]. A suitably functionalised PAT was found to give polarised electroemission in the yellow/orange region when the active layer of the LED was prepared by means of the Langmuir Blodgett technique [151]. the head-to-head connection. In many works.5%. It was suggested [155] that in PDABT. The non planar situation favours the creation of singlet exciton with respect to triplet states leading to an improvement in EL. the tailoring of the electronic properties of PAT was achieved by controlling the regioregularity of the backbone. EL was observed at 541 nm with an efficiency of 0. as high as 24% can only be obtained with the polymer shown in Figure 5. Nature. where different lengths of the side chains do not drastically affect the optical properties. The photophysics of many substituted polythiophenes has been recently summarised by Theander and co-workers [156] who showed that PL efficiency.2´-bithiophenes) (PDABT) having both head-to-tail connections and tail-to-tail connections. 1994. 372.18 at 599 nm.4´-dialkyl-2. in the solid state. Barta and co-workers [152] prepared a poly(4. which is two orders of magnitude higher with respect to previous results on regioregular PAT [153. Inganäs.Handbook of Polymers in Electronics Figure 5.

with an aluminium electrode. a polymer having head-to-tail regularity higher than 90% may be obtained [156]. Stille reaction [162] and using Rieke zinc [163] have been reported. The subsequent reduction of the polymer gives the neutral state [158]. a great amount of work has been done concerning the introduction of electron/hole transporter molecules in the main conjugated backbone and by modifying the architecture of the devices [164-167]. Regioregularity as high as 98%-100% has been reached.Polymers for Light Emitting Diodes C8H17 C8H17 S n Figure 5. much higher than the corresponding device without additives but with calcium as the cathode. The regioregular control with this kind of polymerisation is not extremely high. Introduction of 167 . Careful cleaning of the polymer by many precipitations in methanol has to be done in order to avoid the presence of the iron impurity (acting as dopant). They reported that a device prepared with surfactant-like compounds in poly(3-octylthiophene) gives. A very simple method for reaching high values of regioregularity has recently been reported by McCullough [159] and Bolognesi [160]. PATs are available by three synthetic procedures: (i) Electrochemical synthesis allows the preparation of thin doped films on an electrode. The procedure reported in [157] has been successfully applied to other electroluminescent polymers by the same authors.18 PAT structure exhibiting PL at 599 nm with ηpl = 24% Heeger and co-workers [157] found that high EL efficiencies can be reached by dispersing surfactant-like additives in the active layer. (ii) FeCl3 polymerisation [156] is a simple method to obtain the polymer without many problems. However.03% external efficiency. giving emission in the 700-720 nm range. 0. The starting point is the monomer. As in the case of polymers of the phenyl family. Other synthetic procedures for highly regioregular polymers based on the Suzuki coupling [161]. (iii) With Ni catalyst polymerisation a higher control of the regioregularity can be obtained [154]. 3-alkylthiophene. when the substituent in the 3 position has a high steric hindrance. which is easily obtained.

Besides the electrical anisotropy. Besides the tuning of the properties through proper tailoring of the structures and the cheap technique used to prepare thin and large area films. The development of polarised electroemission is extremely important for optical applications. Dyereklev and co-workers [150] and Ohmari [164] showed that an LED with an oriented electroluminescent polymer as an active layer emits polarised light. 151]. their electrical and optical properties are strongly anisotropic and the chain orientation leads to extremely high electrical and optical anisotropy.1% and 0. For this reason. Stretched (CH)X was reported [169] to have highly anisotropic electrical behaviour with a ratio between the conductivity parallel and perpendicular to the drawing direction in excess of 100.05%. The mechanical stretching of a thin film which has to be assembled between the cathode and anode is the simplest method of orienting polymeric materials. Different methods can be applied to reach a high orientation in the polymers to be used in an LED. polarised EL has recently been the subject of attention for many research groups. It was also observed that a certain tuning of the EL by applying different electric fields may be reached [168]. with respect to other low molecular weight material. The highest dichroic ratios in EL were around 5 with a PPP derivative [125]. that they can be stretched to give highly oriented structures. External efficiencies between 0. So a multilayered structure directly deposited onto the ITO electrode can be used as the active layer of a LED. this technique has the limit of requiring long preparation procedures before reaching an appropriate thickness.4 Recent Developments 5. optical anisotropy can be observed in oriented absorbing polymers. using aluminium as the cathode [167].4. Though the Langmuir Blodgett technique can be used to prepare very well-defined architecture suitable for fundamental studies. Since conjugated polymers are monodimensional semiconductors.01% 168 . polymeric materials have the advantage. These polarisers absorb 50% of the light so that higher light intensities are reached by increasing power consumption. The work by Dyereklev [150] is an example of this approach. 5. It has already been mentioned that the Langmuir Blodgett technique allows orientation of rod-like systems during the transfer process of the monolayer onto the substrates [125.1 Polarised Electroluminescence The opportunities offered by polymeric structures for LED fabrication are manifold. [171].Handbook of Polymers in Electronics Alq3 between the PAT thin film and the cathode increases the EL efficiency up to 0. in backlighting liquid crystal displays (LCDs) the light passes through a set of polarisers in the front and in the back of the active LCD layer [170].

a dichroic ratio in EL of about 12 at 511 nm with a brightness of 200 cd/m2. It has been reported that the procedure followed to reach the high orientation of the macromolecules [174] produces a highly oriented monodomain structure [177] whose morphology has been described as a glassy liquid crystalline monodomain. Grell [145] and Grell and Bradley [174] reported very promising results on the polarised EL obtained with dialkylsubstituted polyfluorene derivatives.4´. 671. Hamaguchi was able to orient alkoxy substituted PPV through the rubbing procedure [172]. the authors mentioned that lifetimes of the devices are strongly decreased. PI film orientation is achieved by rubbing its surface with a cloth as described in literature following a well-established procedure [176].Polymers for Light Emitting Diodes were obtained with an EL dichroic ratio of 2. Perpendicular and parallel refer to the chain orientation (Reproduced with permission from Advanced Materials.19 Polarized EL from a LED having as active layer a highly oriented polyfluorene [145]. deposited on ITO. deposited onto a preoriented polyimide (PI) film. the polarised EL of a device is shown. contained a good hole transporter. 8. reaching a polarisation ratio up to 4.4´´-tris(1naphthyl)-(N-phenyl-amino)triphenylamine to promote hole injection from the ITO to the polyfluorene. through a particular procedure applied to a partially converted PPV precursor. More recently.19. published by Wiley-VCH. 4. In a series of very recent works. This result is very promising and near to the value required for technological applications. Figure 5. so the oriented PI film. Jandkhe and co-workers [173] were able to gain. The EL anisotropy for the peak at 477 nm is 15. 1999) 169 . PI is a good insulator. However. 1999. at the temperature where it exhibits a birefringent fluid phase. 11. In Figure 5. High orientation was reached [175] by heating the polyfluorene films.

The second mirror of the cavity is already formed by the top metal contact (Al or Ag) [186]. Metals constituting the cathode electrodes may react with the active layer causing a change in the structure of the conjugated system. distributed Bragg reflector) between the glass and the ITO layer. The dependence of the emission wavelength on the viewing angle [185. 180]. while hole currents seem not to lead to degradation. Moreover. They were able to measure lifetimes of around 20. 5. The obtained data were explained attributing the main degradation process of the polymer to the passage of electrons.2 Lifetime and Degradation in LEDs All the ‘components’ of a device are prepared with materials that can be chemically reactive. The effect of the microcavity is both to modulate the intensity of the PL or EL of the polymer. In addition. The result is a sharp narrowing of the emission spectrum (see Figure 5. In fact.4. while it is quenched at the wavelengths which are not compatible with the cavity modes.3 Microcavities Apart from the nature of the polymeric active material. increasing the intensity of the light emitted in the forward direction [185]. the structure and size of the LED device play an important role since they determine the coupling of the polymer excitations to the electromagnetic resonant modes. according to its spectral position. Parker and co-workers recently studied the mechanism of degradation in a PPV LED [181]. oxidation of conjugated polymers in the presence of singlet oxygen is reported by many research groups [179. However. 5. the presence of impurities or traces of oxygen has a strong effect in decreasing the overall EL efficiency as well as the lifetime [178]. and simply by adding a mirror (metallic or dielectric.Handbook of Polymers in Electronics The research in this field is very active and even higher polarisation ratios could be obtained in the near future.2 acts as a microcavity. 187] can 170 . In fact. Lifetime is strictly related to this degradation phenomena.20). In fact the polymer emission is enhanced at the wavelengths corresponding to the resonant modes of the cavity. and to modify the spatial distribution of the emitted light. in a single-layer device packaged with a glass cover in a nitrogen atmosphere.4. during continuous operation the luminance of the devices changed in a non monotonic way and the operating voltage increased in a linear fashion.000 hours at luminance greater than 100 cd/m2 when operating in constant current mode. For a planar structure the spatial distribution of the emission considerably narrows. charge injection in polymers introduces reactive species in the backbone and creation of crosslinks between adjacent chains may not be excluded. a device of the type reported in Figure 5. a good resonant microcavity is obtained for typical polymer thickness of the order of 100 nm [182-185].

80. 209.5 Concluding Remarks The rapid growth of this new area of polymer science has stimulated the work of chemists. (Reproduced by permission from Journal of Applied Physics. The exciting results that have been obtained are due to a strong cooperation among different group of scientists used to working in their own field. 1. Microcavities have been very intensively studied because they are good structures for optically pumped lasers [189-196]. Thus. Now there is a common area and this is the reason why this field is growing very rapidly. and also in undiluted sub-micron films [197] for microcavity and planar waveguide structures [198]. and quality factor). In fact. 5. published by the American Physical Society. 1996. and engineers. physicists. The spectral position of the enhanced emission can be varied (within the spectral range of the free space emission) by varying the optical parameters of the cavity (thickness. 1996) be suppressed by introducing proper cavity optical length dispersion [188]. in blends.20 Narrowing of the emission spectrum in a microcavity. linewidth. microcavity structures have been fabricated in order to control the emission energy. many polymers (see Table 1 in reference [195]) showed gain narrowing (spectral narrowing of the PL above an energy threshold of the optical pump excitation) in solution. Further efforts are needed in order to obtain electronically pumped lasers due to the high current densities and problems related to excited state absorption from injected charges [199]. refractive index. thus obtaining different colours with the same material [185].Polymers for Light Emitting Diodes Figure 5. intensity and directionality of many polymeric LEDs. 171 .

Taliani. Inc. Denton. A.L.com.R. Nature. R.T. Bradley. Harrison. R.W.J.-P.com/index. Galvão and S. A.W.. J.L. T. R. Holmes. 1998. 10. K. 1987. Schrieffer and W. Z. Soos. Fincher. T. Brown.K.H. Shirakawa. R. Su. Burroughes.C.D. Bradley and P. 6. K. Gau and A. Brèdas. High vacuum evaporation techniques are generally used for the preparation of the active layer. Inc. J. Marks. Friend. Applied Physics Letters.J. 1367. S.C. www. 847.H.B. M. 1990. S. 539. Eds.A.S. 1994.covion. G. K. Towsend.J.A. Gymer. D. 7. 172 . D. Marks.kodak. 51. D. Reynolds..R.J.D. 1977. C. Skotheim. Nature. Luis. www. Friend in Handbook of Conducting Polymers. R. 121. 397.com A. Köhler.com.A. Polymers offer the possibility of working with a cheap technology giving flexible films that can be bent without breaking and that can be oriented to emit polarised light. Tessler. Logdlünd and W. 2. R.. New York. Lux. Reviews in Modern Physics. 1987. Bradley.B. 1999. J. A. 1998. Burroughes. 5. Heeger. C. Halls. Tasch and W. Graupner in Handbook of Conducting Polymers. Chiang. 39. D. Elesnbaumer and J.G. Advanced Materials. 913. 781.. 347.R.B. Van Slyke. R. Reynolds. Elesnbaumer and J. G. Park. Holmes. 20.cdtltd. A. 6.D.htm.C. Kivelson. 1098.uk.H.D.W.C. References 1. 3.L. N. D. R. 823. Pichler. J. Physical Review Letters. H. Tang and S.co. 102.R.N. Friend. 4. www. J.R. A lot of work has been done with low molecular weight molecules that have been used successfully to prepare good LEDs with very respectable performances.C. H. Wittmann.H.A. 4.F.J.H. E. 249. Y. 8. Dos Santos.uniax. Skotheim. New York. Etemad.N. 9. Friend. R. Marcel Dekker. These are the real advantages of working with polymers and in the near future even better results will be reached.R. A. Marcel Dekker. S. R. www. MacKay. 1997.H. 3. Salaneck. Burn and A. MacDiarmid. C. C. Friend.philips.L.Handbook of Polymers in Electronics The research presented in this chapter is only a part of the field of EL in organic materials. Leising. Towns and H. Solid State Communications. Journal of Physics D: Applied Physics. www. Heeger. 1988.G. Moratti.M. 11. 60. 280. N. Holmes. P. S. Eds. A.

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7771.R. Narayan and G. Salaneck. 1763.S. Polymers for Advanced Technologies. 2. P. 25. C. Khersonsky and R. W. S. Synthetic Metals. Journal of Physical Chemistry B. P. Barta. Fuji. Murthy. 123. M. Nishino. Barker. 68. Mehta. Berggren. 1998. Heeger. T. 164.R. McCullough. H. T. 153. 162. 250.R. 1997. 1996. Macromolecules. Chen. Y. Advanced Materials. R. Advanced Materials. M. Andersson. 157. 7. G. Tada and K. 8. Wu. 9. 1999. N. 155. O. 166. M. 154. G. X. Heeger.H. M.L. Niziol. S.D. Bolognesi. Rieke. Zagòrska. 181 . Iraqi and G. 6. 1999. K. Zannoni and L. 223. 1.J. A. Yoshino. 4. 93. Zagòrska.J. W. Y. 94. P. McCullogh. Rieke. J. F. Fannig. Ostergard and H. Chemical Physics Letters. Tripathy. Journal of Materials Chemistry. Cao. 151. 159. 1996. 8. Paloheimo. 406. 11. Guillerez and G. 156. Zyung.A. M. Y. S. Theander. 1999. 119. Svensson and M.L.D. 161. Macromolecules. T.Polymers for Light Emitting Diodes 150. W.D.M. A. Sanetra and M.D. 276. T. N. G. Pròn and S. Inganäs. 160. 1998. G. 165.A. D. Advanced Materials for Optics and Electronics.D. 403. Yu. Wennerström. 152. A. P. Journal of Materials Chemistry. Loewe. Synthetic Metals. 441. 1994. Chen and R. L. 1998. G. W. 3. Olinga. 158. A. Jung. 1995. T.W. Bidan. Lee and S. Chen and R. 7. R. Porzio. Stubb. J. Inganäs. A. Barta. O. Hjertberg and O. 1990. 1998.S. 11. A. 1997. Dyereklev.K. 243.G. Bajo. 103. 12. 151. Eckert and F. 121. 1. Andersson. Bolognesi. Synthetic Metals. Advanced Materials. Yoshida.J. Wudl. Bajo. Synthetic Metals. Souto Maior. 1268. 1999. Mammo. Hironaka. 24. 10. 50. Acta Polymerica. 7671. 1996. K. 23. 6. Takiff and R. 3.M. T. 29. 917. Advanced Materials. 43. 1997. Kim. 100. Hinkelmann. Yu and A. Ohmori. 163.

Synthetic Metals. Woo. Hayes. 183. Shirakawa.P. M. Parker and F. Y. Smela. A. Brehmer. R. 53. Advanced Materials. Grüner. G. A.C.G.J. M. Slusher and J. Grell. Advanced Materials. Zuppiroli. 9. 277. Phillips. Leclerc. Cecchinato. A. Bradley.E. Smith and C.M. 168. Hollering. Kaminorz. 261. Synthetic Metals. Sdiove. Skolnick. L. 60. 1994. M. 56. Remmers. I. I. Heeger. M. M. Z. 69. 173. F. 175. 1999.W. M. 12. Dodabalapur. Inganäs and L. F. 765. 395. Physical Reviews B. Journal of Applied Physics. M.A. 6954. Y. Abdou. Weder.Cao and C. S. L. 67. 964. B. Grell. C. Virgili.Handbook of Polymers in Electronics 167. Yoshino. Orfino. Bradley and M. and H. J. 80. van Aerle. P. 177. 11. 179. Bolognesi. 181. Nature. Park. 183. D.D. 177. M. K. 170. Romero. T.C. W. 172.D. 830. E. 3381. Adès. Schaer. Miller.H. Brütting and M. Yang. Bradley. Jandke.W. 1993. D.C. Advanced Materials. 81. 169. 3111. 1998. Y.Y. 1997. 9. C. Cacialli and R. 1995. 1997. 392. Physical Reviews B. 171. Barmentlo and R.S. B. Applied Physics Letters. 798. Yoon. 176. V. Hamaguchi and K. A.T. Nature. Cocchi. 106. Advanced Materials. L. D. Schartel.C. 74. Bastiaansen. M.J. 271. 2441. 182 . 80. Synthetic Metals. V. 1997. M. 10. Synthetic Metals.D. Grell and D. Moutali. O. Xie. 6. R. 1997. Deen and S. M. Botta. Neher. 1998. Holdcroft. 1999.D. Cumpston. D. 1996. Fattori and M.A. Park. 79.S.R. 8. Hennecke. D. M. Rothberg.O.J. 3716. 184. Inbasekaran and E. T.B.P. Whittaker.J. J. 180. Jensen. Akagi.H.W. Advanced Materials. 1999. Wachtendorf. 111. 1998. 182. M. 85. P. Schoerer.J. Reghu. A. 178. D. 895. 174. Journal of Applied Physics. Bradley.D. Strohriegl. N. 2000. Phillips. 4798. 10. Jordan. 1999.B.M. Applied Physics Letters. E. Parker. 1996. 10. Journal of Applied Physics.D. 1995. M. Lidzey. Gmeiner. C.M. D. Walker and D.M.

24. McGehee. 547. 533. Lidzey. M.F. 193. Stagira. Journal of Applied Physics.R. Hayes. Stevens and R. B. 194. Bleyer and D. Denton and R. Alvarado and P. Denton. H. Nature. V.J. 56.B. S. 192. 389 195. 2308. Leising. Bradley. Gong. Applied Physics Letters. Hide. 10. 80. 1997. Bradley.A. Friend. Bulovic.C. Díaz-García.Polymers for Light Emitting Diodes 185. 382. Schwartz and A. Applied Physics Letters. Friend. Zavelani-Rossi. 187. 430. C. P. Srdanov and H. 1997. S. 1997. R. R4363.G. 7.D. V.J. Advanced Materials. Miller. N. Lanzani. S. 186.V. 73.H. Gupta. 2860. Synthetic Metals. 3492. W. Sastre and A.F. M. Grüner. Shkunov. Journal of Applied Physics. Applied Physics Letters. D.V. S. A. V. Becker and R. 556. 1997.E. 191. Applied Physics Letters. 695. Seidler. J. Kozlov. Friend. You and M. Zenz. Yoshino. 1997. Rothberg and T.M.D. De Silvestri. 2.H. Tessler. Grüner. 197.G. 1998.H. 207. Advanced Materials. 1995. A. 5. 9. J. Y.T. 8. 198. P. M. 198. R. 12.C. G.D. 70.R.G.J. Burns. Stevenson.Y. Accounts of Chemical Research. Z. V. Wang. Dodabalapur. G. 84. 386.J. 1996.R. 20. 196. 4096. 30. 1996. Burrows and S. 65. Cacialli. Penzkofer. Friend. S. Frolov.E. A. Holzer. A. Nisoli. Heeger. Physical Reviews B. L. V. Burrows. Cacialli and R. 190. G. 974.H. Tessler. Friend. G. 189. M. 135. Dogariu. Forrest. Park. 8. Mataloni and G. V. 84. F. 1997. Bulovic. Nature. Advanced Materials. 7. P. 8. G. M. Phillips and R. F.J. 1997. 1994. 1998. M. 199. D. Costela. F. J. Forrest. S-H.E. Khalfin. Tessler. S. Kozlov. M. 73. Paethasarathy. 183 .H. Nature 1996. N. 188. M. Vardeny and K. Thompson. Baldo. 1998. N.A.

Handbook of Polymers in Electronics 184 .

leading to a demand for sub-micron device geometry. Dubois 6. have been improved. This evolution of the minimum size of the VLSI is known as More’s law and can be represented by Figure 6. thin films of semiconductors.1. In addition. This trend to miniaturisation is continuing.6 Photopolymers and Photoresists for Electronics J.-C. switching speed and reliability.1 More’s law showing the evolution of the minimum size of VLSI versus year 185 . permitting the manufacture of integrated circuits with several millions of discrete transistors working at frequencies reaching GHz. Integrated circuits consist of patterned. metals and dielectrics on a semiconducting substrate such as silicon or gallium arsenide. Today the so-called very large scale integration (VLSI) technology is used. such as power consumption. Figure 6. This has given rise to a continuous increase in chip size and in the density of components combined with a reduction in their cost.1 Introduction There has been tremendous progress in integrated circuit technology since its beginning about 25 years ago. other characteristic parameters.

Depending on the wavelength of the irradiation.8 4 (6.1.1 Microlithography techniques Technique Contact (vis.5-1. Electron-beam lithography is already used commercially for fabricating master masks for photolithography. One can expect the development of deep-UV lithography techniques at 193 nm giving line dimensions as small as 0. Table 6.Handbook of Polymers in Electronics Such resolution cannot be reached by using conventional (or near-UV) photolithography because of diffraction phenomena.24 >0.9-2.35 >0. usually a polymeric film (0. X-ray lithography and ion beam lithography are under development. Here other technologies with potentially higher resolution such as deep-UV photolithography. The formation of the desired patterns on the substrates requires the use of a resist coating in which the pattern is first generated. The different techniques of lithography are summarised in Table 6.2-4.30 >0.1 186 .5-5 0.7 >0.0 μm thick) is spin-coated onto the substrates and then exposed to radiation.8) Pros Global exposure Steppers Steppers No vacuum necessary No vacuum necessary Global exposure Direct writing Limited resolution Resist to be optimised Resist sensitivity Vacuum necessary Cons Sensitivity to visible Limited resolution Resolution (μm) >0.5-2 x 103 E(eV) 3.01-0.12 >0.1 <0. necessary for the latest VLSI.02 (corresponding to an associated wavelength λ) 2500-250 0.12 μm.6 2. One of the key points for obtaining high resolution is to obtain polymers with sensitivities well adapted to the chosen type of radiation and with response speeds which allow high production rates. The resist layer.UV) g-line i-line Deep-UV Deep-UV X-ray E-beam λ (nm) 320-480 436 365 248 193 0. electron-beam lithography. different minimum linewidth are obtained.1 Ion-beam High resolution Vacuum necessary <0.

6. 2] In order to have a better understanding of a resist’s requirements.2 Microlithography Process [1. In the example shown in Figure 6. Figure 6.2. 4]. consisting of SiO2 on Si [3. the resist is applied as a thin film to the substrates.Photopolymers and Photoresists for Electronics This chapter describes some aspects of polymeric resist materials for microlithography allowing the necessary dimensions of VLSI to be reached.2 Microlithography principle 187 . a description of the different processing steps used in microlithography is necessary.

followed by baking in order to eliminate the residual solvent and to suppress mechanical stress.3 The different lithographic methods: contact.2 Exposure In this step. In the contact mode the mask is in contact with the substrate to be treated. The recent development of excimer lasers emitting in the deep-UV region has introduced the use of deep-UV radiation (150-300 nm). 8. The lithographic method could be contact. Figure 6. generally through a mask. Some attempts have been made to deposit polymeric films by the plasma deposition technique [5]. while in the projection mode the image of the mask is projected on the substrate.1 Resist Coating Polymeric resists are usually deposited on the substrates by spin coating. and especially the 248 and 193 nm wavelengths [7. The steppers use classically a high-pressure mercury lamp with two radiations: i-line (436 nm) and gline (365 nm). to one of the following types of radiation: UV light (including recently deep-UV). proximity or projection mode 188 . The source of radiation is generally a mercury lamp or a mercury-rare gas (xenon) discharge lamp. 6. The projection mode is the best method for VLSI production since it allows more precision and involves less deterioration of the mask. ions. Figure 6.Handbook of Polymers in Electronics 6. 9].3. proximity or projection mode [6]. This gives a maximum of radiation in the 350-450 nm range.2. electrons or X-rays. In the proximity mode there is a gap between the mask and the substrate.2. the resist layer is exposed.

the resist consists of an inert matrix resin and a radiation-sensitive molecule called a sensitiser. In two-component systems. the use of a solvent may cause swelling and may lead to a lack of adhesion of the resist to the substrate. However.3 Development Development is an important step of the process. which is widely used in circuit manufacture and dry development. resists have been divided into two classes depending on their behaviour upon irradiation: positive and negative resists (Figure 6. which is usually.3.Photopolymers and Photoresists for Electronics The resist contains radiation-sensitive groups which undergo chemical reactions when exposed. Development transforms the latent image into an image serving as a mask for etching of the substrates. Two technologies are now available: wet development. leading to the formation of a latent image which closely matches the pattern of the mask. the structure of the polymer contains the radiation-sensitive groups either in the main chain or in the side chain. and (iii) polarity change of the polymer. These problems may be solved by using dry development techniques which have recently been introduced. a low molecular weight compound. Organic-based resists have been classified according to whether they consist of one or two components.2.3. 6.1 Wet Development Wet development can be based on three different types of radiation-induced changes: (i) variation in molecular weights of the polymers (by crosslinking or by chain scission).2).2. since it is one of the keys for obtaining a well-defined pattern on the substrates.2. which is still under study. (ii) reactivity change. 189 . Traditionally. In one-component systems. 6. Positive resists become more soluble in the irradiated area relative to the unexposed area whereas negative resists become less soluble in the irradiated area relative to the unexposed area. 6.2 Dry Development Dry development may be achieved using either a vapour phase process or a plasma (usually oxygen plasma).

6 Resist Removal (Stripping) The main goal of this step is the complete removal of the resist without affecting the wafer surface.2. 6. Two methods are used: wet stripping (the use of either solvents. This limitation is due to the isotropy of the process.2. The cycle described in this section has to be repeated several times to obtain the integrated circuit component. reactive ion etching (RIE) and sputter etching. 6. or oxidisers that transform the resist into carbon dioxide and waste) and plasma resist stripping. to improve adhesion between the resist and the substrate and chiefly to increase the resistance of the resist to the subsequent etching process. However.2. sensitivity to radiation and contrast. 6. adhesion. 6. which makes linewidth control difficult for features less than 2 μm when thick substrate layers are used.4 Post Baking Post baking is used as a post-development step to eliminate the residual development solvent. gives rise to less pollution and leads to integrated circuits with higher densities than does wet etching..Handbook of Polymers in Electronics 6. As a rule. boron.3 Resist Requirements The main requirements of a resist are solubility.2. 190 . 3] The most common method of pattern transfer to the substrate is by wet chemical etching. all semiconductor wet etching processes exhibit the same basic limitation. which dissolve the resists. etch resistance. arsenic) diffuse into the stripped regions of the semiconductor substrates. aromatic polymers resist plasma etching better than aliphatic polymers.7 Doping During this step very small amounts of ‘impurities’ (e.g.5 Etching [1. Dry etching is more economical. The need to transfer fine features in thick substrates has led to the development of anisotropic etching techniques such as plasma etching.

J/m2). throughout the various steps of integrated circuit manufacture. is related to the ability of a polymer to give vertical sidewalls. The parameters are determined from the sensitivity curve of the resist. σ0. 6. Sensitivity is said to increase as the dose required to produce the lithographic image decreases. The sensitivity of a negative resist is conventionally defined as the dose at which 70% of the original film thickness has been retained after development. Most dry etching techniques involve a high radiation flux and temperatures often higher than 80 °C.. γ. 6.Photopolymers and Photoresists for Electronics 6.1 Solubility Resists are generally deposited onto substrates by spin coating. 6. σ. The sensitivity of a positive resist. aromatic structures) have higher dry etch resistance. The required sensitivity varies with the type of irradiation and is expressed as energy/surface (e.g.4(b)). silicon nitride or semiconductors.3. Polymers exhibiting high Tg values and containing radiation stable groups (e. The contrast.2 Adhesion The resist must possess good adhesion properties to various substrates. is the dose required to achieve complete solubility of the exposed region under conditions where the unexposed region remains completely insoluble. such as metal. as a function of log10 (Dose) (Figures 6.7.4(a) and 6. er/e0 (er is the thickness after development and irradiation. σ0..3 Etching Resistance Wet chemical etching requires good adhesion and chemical stability of the resist towards acidic or basic etching solutions. silicon dioxide.4 Sensitivity and Contrast The sensitivity. Resolution (defined as the smallest linewidth which can be achieved) depends on the contrast. solubility in organic solvents is necessary. is related to the ability of a polymer to undergo structural modification on irradiation.3.g. For a negative resist: γ = (log10 σ1/σ0)-1 (6.3. which expresses the normalised film thickness. Poor adhesion leads to loss of resolution. e0 is the initial thickness of the resist).1) 191 .3. therefore.

2) Table 6. this dose is expressed as a current density around 5-10 mC/cm2.Handbook of Polymers in Electronics (a) (b) Figure 6. For electron beam lithography. Negative resists are in general more sensitive than positive resists but they exhibit a lower contrast (γ<1) (Table 6. A contrast higher than 3 is generally required for the high circuit density of new generation technologies such as the 256 Mb DRAM.4 Typical sensitivity curves for negative and positive resists and for a positive resist: γ = ⎜(log10 σ1/σ0)-1⎜ where σ1 is the dose required to reach the required thickness after development. values of the doses for the i. from 10-20 mJ/cm2.and g-line vary from 10-50 mJ/cm2 and for deep-UV.2). (6. For narrow-UV radiation.2 Parameters affecting the characteristics of photoresists Characteristics Radiation sensitivity Contrast Resolution capability Resistance to etching Stripping capability Positive low high high low high Negative high low low high low 192 .

which no longer inhibits dissolution of the novolac polymer in aqueous base [4] (Figure 6. This reacts with water to produce the base-soluble indene carboxylic acid.Photopolymers and Photoresists for Electronics 6. several process variations have been reported aimed at reversing the tone of the image so that the resist would act as a negative resist [11. The most significant advantages of this family of photoresists are the lack of swelling during the development step.1 Conventional Photoresists Photolithography using light in the wavelength range 350-450 nm is the technology currently used in the manufacture of integrated circuit devices. The most interesting process is probably that described by Moritz and Paal [13] and known as the Monazoline process.4. the polymeric material is a low molecular weight novolac polymer (Figure 6.2-diazonaphthoquinone (DNQ) (20%-50% by weight).1 Positive Photoresists All near-UV positive photoresists are two-component systems. DNQ forms a complex with the phenol groups of the novolac resin and prevents the dissolution of the latter in an aqueous base.5 Novolac polymer Exposure of the resist to UV light results in photodecomposition of the sensitiser to an unstable ketocarbene.4 Resist Materials 6. Figure 6. a good resolution in thick coating and wellknown film forming properties. There are many commercially available positive photoresists. 193 . Since swelling does not take place during the development of positive photoresists. which differ slightly from one another. 12]. and the sensitiser is a derivative of a 1.

4. a range of commercially available detergents (1-hydroxyethyl-2-alkyl-imidazolines). UV sensitive groups.2. UV irradiation gives rise to crosslinking. are included in the main chain or in the side chain of the polymer. such as chalcone.2 Negative Photoresists 6. it is based on the thermal decomposition of indene carboxylic acids in the presence of amines such as monazolines. etc. cinnamate.Handbook of Polymers in Electronics Figure 6. 6. p-carboxycinnamate.1.2-diazonaphthoquinone The process is outlined in Figure 6.6 Photodecomposition of 1. p-phenylene-bis acrylate and styrylpyridinium.7. which is the key process occurring in the KPR resist (Kodak).1. 194 . The crosslinking of poly(vinylcinnamate) [14].1 One-Component Systems In this type of photosensitive system.. is shown in Figure 6.4. diphenyl-cyclopropene carboxylate.8. styrylacrylate. cinnamilidene malonate.

a negative resist which crosslinks through the double bonds under irradiation 195 .Photopolymers and Photoresists for Electronics Figure 6.7 Monazoline process: the thermal decomposition of the carboxylic acid in presence of the monazoline base transforms the acid into an insoluble indene derivative leading to a negative resist (reverse tone process) Figure 6.8 The KPR resist.

4-polyisoprene in the presence of a Lewis acid (ZnO2.4-polyisoprene The photochemical transformations of a bisazide sensitiser leading to the crosslinking of a cyclised cis-1.9).4-polyisoprene is obtained by heating 1.2.4-polyisoprene.4-polyisoprene are shown in Figure 6.4. 196 .2 Two-Component Systems Negative near-UV resists are derived mainly from photoinduced crosslinking of partially cyclized cis-1. An insoluble three-dimensional crosslinked network is obtained.Handbook of Polymers in Electronics 6. There are several different possible reaction mechanisms.9 Formation of cyclised cis-1. SnCl4) (Figure 6. Cyclised cis 1.10.10 Photochemical transformations of a bisazide sensitiser in a carbene leading to the cross-linking of cyclized cis-1. Figure 6. Figure 6.1. AICI3.4-polyisoprene with bisazido sensitisers [15].

That is why there is now a great interest in excimer lasers [1.25 μm linewidth generation. 197 . which have output wavelengths of 222. 6. respectively.11). positive resists are usually preferable. The excimer lasers are mainly lasers based on KrCI. for high resolution circuits.18 μm linewidth generation. p(PMMA-OM-MAN) (Figure 6. Poly(methyl methacrylate-co-3-oximino-2-butanone methacrylate-co-methacrylonitrile). One of the problems of deep-UV photolithography is the low brightness of mercury arc lamps. allowing good masking speed.Photopolymers and Photoresists for Electronics These resists are commercially available and are able to meet the requirements of most integrated circuit designs. Resolution limits in the 0. KrF and ArF. The main limitation of negative resists of this type is their dependence on organic solvent developers. Aromatic moieties ensure a useful plasma etch resistance. Poly(aromatic sulfones) may also be used as positive resists [19].1 One-Component Systems One-component positive resists are essentially copolymers or terpolymers derived from PMMA. KrF exposure systems (step and repeat) already exist commercially and are used for 0. since the diffraction-limited resolution of optical projection printing tools is proportional to the exposure wavelength. 249 and 193 nm. which cause resist image distortion as a result of swelling. 17] as intense deep-UV sources.5-0. The sensitivity of this terpolymer is 170 times that of PMMA and is capable of sub-micron resolution. However.4.1 Positive Deep-UV Resists 6. 6.12 μm. Copolymer structures are chosen in order to increase the low value of the absorption coefficient of PMMA at 215 nm. Comonomers are selected either to absorb in the 230-280 nm range or because they contain a photosensitive chromophoric group. KTFR (made by Kodak) is a negative resist of this type.4. sensitised with t-butyl benzoic acid requires an exposure dose of less than 30 mJ/cm2 [18].1. But most emphasis has been recently put on the 195 nm exposure systems for 0.4. Their sensitivity is high.2. That is to say that new exposure sources and/or very sensitive resist materials must be developed. 16.25 mm range may be expected. which are the most common exposure sources. however.2 Deep-UV Photoresists Interest in deep-UV photolithography (150-280 nm range) lies in the possibility of obtaining higher resolutions than cannot be achieved with conventional optical technology. For example.2. The next generation of components will require linewidths below 0. Their quantum efficiency is low.

1. In this case.4.2 Two-Component Systems Several attempts have been made to design two-component deep-UV positive systems with increased sensitivity. Wilkins and others [21] have described another system.11 Terpolymer of PMMA sensitive to 240 nm radiation 6. 198 . which is bad for the sensitivity.12 Meldrum’s acid is converted to a volatile compound under irradiation at 250 nm The resist exhibits reasonable sensitivity. An example is a system based on a novolac polymer and 5diazo Meldrum’s acid as a dissolution inhibitor [20]. This system exhibits a good photosensitivity (100 mJ/cm2 in the 230-300 nm range) with a very high contrast (g>5). the novolac resin itself has a strong absorption around 310 nm. the resin is a copolymer of methyl methacrylate and methacrylic acid (which is transparent above 260 nm and which is soluble in aqueous alkali) and the dissolution inhibitor is an o-nitrobenzyl carboxylate. Figure 6.2.12.Handbook of Polymers in Electronics Figure 6. which is converted to volatile compounds on irradiation according to the scheme shown in Figure 6. The Meldrum’s acid derivative provides a bleachable chromophore at 250 nm. However.

14) generates benzene sulfonic acid. 6. absorb too much and give bad contrast when used as deep-UV resists in the 248-193 nm domains.2. such as diphenyliodonium hexafluoropropane sulfonate.13). Figure 6. T-BOC) leading to positive resists [22].4.2.1. [44].4. which generates trifluoromethane sulfonic acid. The acid generated decomposes the T-BOC group. 199 . Very good results are obtained with the use of a different approach to photoactivation using the t-butyl carbonate (T-BOC) group. See. for example. This group is fixed on a polymer and used with an acid photogenerator.1. leading to a soluble polymer. such as AsPF6–.2. Onium salt photoinitiators of this type can induce cationic photopolymerisation under photoirradiation.2. The i-line and g-line resists. such as novolac resists.13 Example of an acid photogenerator Other acid photogenerators are used. The reaction is complex and several products of this type are used with Lewis acids.g.2 Acid Photogenerators A typical acid photogenerator is triphenyl sulfonium triflate (Figure 6.. AsF6– and BF4–. or bis-(diphenylsulfonyl)diazomethane. The latter (shown in Figure 6.1 t-Butyl Carbonate (T-BOC) Photoresists The progress in two-component systems is due to the combination of two things: • • an acid photogeneration and a polymer with labile groups sensitive to the acid (e.Photopolymers and Photoresists for Electronics 6.

Handbook of Polymers in Electronics Figure 6.4. e. a copolymer of 4-hydroxystyrene with a t-butyl acrylate and a phenyloxysuccinimid as the acid photogenerator. Figure 6.14 Bis(diphenylsulfonyl)diazomethane 6.2. CO2 and isobutylene is evolved (Figure 6.. Derivatives of this resist system have also been proposed.3 T-BOC Polymers Different types of T-BOC polymers have been synthesised and are used in association with the photoacid generators. However. The TBOC-PHS is decomposed by the acid generated by the photoacid generator.15).2. A resist made with poly(p-tert-butoxycarbonyloxystyrene) (T-BOC-PHS) and an onium salt was first described by IBM Laboratories [49].15 Decomposition of T-BOC-PHS in an acid medium The resolution of the system is moderate and the stability after irradiation is poor.g. This resist is more stable during processing (Figure 6.16). An evolution toward the lower wavelength is in progress with the use of the 193 nm ArF laser source.1. Optical absorption requirements demand new resist polymers with no 200 . it is used for the 243 nm domain due to its sensitivity.

17a and 6. The MRS is composed of a phenolic resin and a bisazide [24].16 μm lines and spaces has been demonstrated. Polyacrylates seem adapted to this wavelength.Photopolymers and Photoresists for Electronics Figure 6. such as adamantine.16 Copolymer of t-butyl acrylate and 4-hydroxystyrene used as a deep-UV resist aromatic structures. has proposed a resist with alicyclic radicals for use in 193 nm microlithography (Figures 6. which avoids the swelling phenomena.17b).4. a subsidiary of Clariant Corporation.2 Negative Resists Microresists for shorter wavelengths (MRS) are developed in an aqueous base.17a Mechanism of degradation of the photoresist AX 1000 6. are used on the polymer [49-56]. AZ Electronic Materials. 201 . Figure 6. For this reason alicyclic radicals. Resolution of 0.2. but the lack of aromatic structure gives poor resistance to plasma etching.

Examples are summarised in Table 6.Handbook of Polymers in Electronics Figure 6. positive or negative electron-beam resists have to possess the following properties: • Be able to exhibit sub-micron resolution (resolution being affected more by backscattering of electrons than by diffraction effects since the de Broglie wavelength of electron beams is of the order of a few tenths of an Angstrom). In addition to the usual requirements discussed earlier.3.4. The resolution is better than 0. 202 .15 μm. (Picture courtesy of AZ Electronic Materials. a business unit of Clariant Corporation) Many other deep-UV negative resists have been reported.17b Lithography results with AX 1000 at 193 nm. 6.3 Electron-Beam Resists The major advantages of electron-beam lithography over conventional photolithography are a higher potential resolution and the possibility of direct beam writing on the resist surface.

owing to the presence of quaternary carbon atoms. and Be sufficiently stable to withstand dry etching as well as wet etching.6-Di(4azido benzylidone)4-methylcyclohexanone 100 ONR20 25 Chloromethylated polystyrene None 40 26 • • Have a sensitivity of the order of 10-6 C/cm2 (at 10-30 kV).3. but it exhibits rather low sensitivity (50 μC/cm2 at 15 kV) and poor resistance to dry etching techniques.3′ Diazidodiphenyl sulfone 50 RD2000N 24 Poly(methylisopropenylketone) (PMIPK) 2.4. When subjected to electronbeam irradiation.3 Some examples of deep-UV negative resists Resist Structure of repeat unit Sensitiser Sensitivity relative to PMMA 60-450 Tradename Ref. Cyclised polyisoprene See Figure 6.9 Bis-azide UR 110ODWR 23 Polyvinylphenol (MRS) 3. PMMA is an excellent positive resist from the viewpoint of adhesion and resolution. 6.1 Positive Electron-Beam Resists PMMA was one of the first positive resists to be investigated.Photopolymers and Photoresists for Electronics Table 6. 203 . PMMA suffers extensive main chain scission.

Some examples are given in Table 6. Toray Industries) 5. Substitution either on the quaternary carbon (using polar electronegative substituents) or in the side chain may do this. 204 . By copolymerising methacryloyl chloride and methacrylic acid with methyl methacrylate. In order to improve the thermal stability of PMMA.Handbook of Polymers in Electronics Table 6. Daikin Kogyo) 106 93 3-12 29 Poly(trichloroethylmethacrylate (EBR-1. Daikin Kogyo) 5x105 50 0.5 31 One way to increase the sensitivity of PMMA in electron-beam lithography is to weaken the main chain stability of the polymer.4 27 Poly(dimethyltetrafluoropropyl methacrylate) (FPM.18).4. Roberts [32] has described a twocomponent electron-beam resist.25 30 Poly(ethylcyanoacrylate) 2x105 1.5x105 138 1. Poly(hexafluorobutylmethacrylate) (FBPM-110.4 Some electron beam positive resists Resist Structure of repeat unit Molecular weight Tg Sensitivity (°C) 20 kV (μC m-2) Ref. it is possible to form intermolecular crosslinks (acid anhydride bonds) in situ on the appropriate substrate by heating the resist after spin coating (Figure 6.

6 μC/cm2 at 20 kV) and is commercially available. and the exposed regions become soluble.18 Crosslinking through an anhydride [32] Electron-beam irradiation breaks the acid anhydride linkage. Poly(2-methyl-1-pentene) undergoes spontaneous depolymerisation during irradiation leading to gaseous compounds.20 have good oxygen plasma resistance. 205 . 36] at Lucent Technologies.19). are another important class of positive resists. a two-component system consisting of a novolac resin (known for its excellent dry etching resistance) and poly(2-methyl-1-pentene) (acting as a dissolution inhibitor) has been designed by Bowden and others [35. In order to improve the etch resistance. Poly(butene-1-sulfone) shows the best properties (σ = 1.19 Mechanism of the degradation of polysulfone by electron-beam irradiation Unfortunately. thus restoring solubility to the irradiated areas. alternating copolymers of sulfur dioxide and an olefin.Photopolymers and Photoresists for Electronics Figure 6. USA. which exhibit a very high sensitivity [35] owing to the weak carbon-sulfur bond (see Figure 6. Resistance to plasma and to developer solvent is improved by the anhydride crosslinking. presumably due to the conversion of Si to SiO2. Several systems derived from that of Roberts have been studied [33. Poly(olefin sulfones). poly(olefin sulfones) are not sufficiently stable towards dry etching. Figure 6. Resists having the structure [37] shown in Figure 6. 34].

The different structures of these polymers are given in Table 6.3 1. 38 39 40 41 3.8x105 2x105 5. However.4.9x105 Sensitivity 20 kV (μC m-2) 0. 206 .5. are given in Table 6.5 Ref.2 Negative Electron-Beam Resists The chemistry of negative electron-beam resists derives from the ability of epoxy.4.5x105 2. 42 COP = copolymer of ethylacrylate and methylmethacrylate GMC = poly(glycidylmethacrylate-co-m-chlorostyrene) P(ETMA-co-MMA) = poly(ethylthiomethacrylate-co-methylmethacrylate) PCMS = poly(m-chloromethylstyrene) PVMS = poly(methylvinyl siloxane) 6. X-ray masks are difficult to fabricate with sufficient yields.Handbook of Polymers in Electronics Figure 6.6 4 0.6 0. Resolution in X-ray lithography will never do better than the resolution of the electronbeam exposures used to make the masks.5x105 4.4 X-Ray Resists X-ray lithography is an extension of near-contact lithography for replication of 1 μm and smaller geometry. vinyl(allyl) and halogen (particularly chlorine) groups to promote crosslinking. since X-rays cannot be focused or deflected.5 Some negative electron-beam resists Resist COP GMC P(ETMA-co-MMA) PCMS PVMS Structure of repeat unit Acrylate Epoxy acrylate Thiirane acrylate Polystyrene Polysiloxane Molecular weight 1. the inherent sensitivity of these reactive moieties incorporated into the polymer is well within the required exposure range of most electron beam exposure machines. episulfide. Characteristics of some examples of negative electron-beam resists. Incorporation of aromatic groups into the polymer improves the dry etch resistance and the resolution of negative electron-beam resists.3.20 Poly(olefin sulfone) resistant to plasma etching 6. Table 6.6. including poly(acrylate) and polystyrene derivatives.

34 Å [48] 207 .6 Formulae of some negative electron-beam resists COP PVMS GMC P(ETMA-co-MMA) PCS For technological reasons. the energy flux deposited at the wafer is low.Photopolymers and Photoresists for Electronics Table 6.21. A typical sensitivity curve of fluorinated polymethacrylate (FPB) in comparison to the curve of PMMA is shown in Figure 6. Figure 6. so highly sensitive resists (σ<10 mJ/cm 2) are required.21 Comparison of the sensitivity curve of a FPB resist (σ = 70 mJ/cm2) with that of PMMA (σ = 360 mJ/cm2) at X-ray irradiation of 13.

The aim of the multilayer resist technology is the simultaneous achievement of good linewidth control. Figure 6.5.. they offer interesting advantages for including inorganic atoms which could be transformed into oxide (e.4. Highresolution patterns are generated in the thin top layer followed by pattern transfer into the thick bottom layer (bilayer resist systems). called the isolation layer.Handbook of Polymers in Electronics It can be said that positive or negative resists developed for electron-beam lithography can be used for X-ray lithography.g. 6. The main feature of multilayer systems is the separation of imaging and step-coverage functions in different layers.5 Special Resists 6. Highly sensitive positive X-ray resists are not really well adapted at this time since they do not possess all the required sensitivity and masking properties.22 Bis-acryloxybutyl tetramethyl disiloxane (BABTDS) used for photolocking The sensitivity of this system is 1. the sensitivity of conventional electronbeam resists is not sufficient from an economical point of view. The resist consists of a plasma-degradable acrylic polymer (poly(2.23). The highest X-ray resist sensitivity has been obtained by using an elegant resist technique referred to as ‘photo-locking’ [47]. these requirements cannot be met simultaneously since good step coverage and leveling of topography variations on the wafer surface require a thick resist while high resolution is obtained with a thin resist. Sometimes. This process is referred to as a tri-layer resist system (Figure 6.22) which can be readily polymerised by the absorbed radiation. preventing mixing of these products.4. a third layer.5 mJ/cm2. is introduced between the two. However.3-dichloropropyl acrylate)) and a volatile silicon-containing acrylate (bis-acryloxybutyl tetramethyl disiloxane. However. 208 . Figure 6.1 Multilayer Resists The multilayer resist (MLR) strategy was introduced by Lin and co-workers [16. silica). The X-ray masking technique itself suffers from problems such as the difficulty of mask manufacture. Generally. high resolution and good step coverage. 17] and called ‘portable conformable masking’ (PCM).

most polymers do not possess sufficient etching resistance to withstand oxygen plasma etching of the thick hard-baked resist layer during the process of a multilevel system. These are used as insulation layers in microelectronics due to their good dielectric properties.Photopolymers and Photoresists for Electronics Figure 6. 6. the sensitive group R allowing photocrosslinking is an acrylate ester. the crosslinked patterns are converted into polyimides by heating. This product is now developed by CIBA (Probimide. as shown in Figure 6. Selectilux HTR) or DuPont.4. After development. e.g.1 Negative Polyimides Most of the negative polyimides are based on the principles of the pioneering work of Rubner [58]. Examples of some silicone resists are shown in Table 6.4. However. This has led to an extensive use of silicon-containing polymers since these materials are known to convert into SiO2 in oxygen plasma and thereby to exhibit high tolerance to oxygenreactive plasma etching. 6. Photoresists based on polyimides are very attractive because they allow direct patterning of the polymer. A soluble polyamic acid precursor carries a photo-reactive group sensitive in the 250-450 nm range able to crosslink under irradiation..7. In the system of Rubner.5.24. The acrylate is eliminated during subsequent heating. 58] Polyimides are interesting thermally-stable polymers which could resist at high temperatures (more than 300 °C).23 Multilayer resist system Some resists that have been previously described may be used in MLR technology. a novolac-type resist for the imaging layer and PMMA for the planarising layer. 209 .2.2 Polyimide-Based Photoresists [57.5.

25).8 [57]. 6.5. The different characteristics of polyimide-based photoresists are represented in Table 6.4. One example starts from a soluble polymer [60] with a formulation analogous to a novolac positive resist.7 Silicon-containing polymers used in multilayer resists Structure Radiation Company Reference Electron-beam IBM 43 Deep UV IBM 44 Electron-beam X-ray Deep UV NTT 45 Near UV NTT 46 Other types of photosensitive groups have been used.Handbook of Polymers in Electronics Table 6. o-naphthoquinone diazide was used as a photoreactant linked to the polymer (Figure 6. 210 .2 Positive Polyimide Resists Positive polyimide resists have also been developed. Yoda and Hiramoto [60] reported a negative photopolyimide having photosensitive groups introduced to polyimide precursors through acid-amine ion linkage.2. Toray developed this product.

25 Example positive photopolyimide resist material 211 .24 Formation of polyimide.Photopolymers and Photoresists for Electronics Figure 6. the polyamic acid is crosslinked by radiation through the acrylate and cyclised into polyimide by heating at 200 °C after development Figure 6.

USA.Handbook of Polymers in Electronics Table 6. 3.5 7.1 μm or less with sources like electron-beam. S = ester (2) Decrease of the film thickness during baking 6. 4. Marcel Dekker. 1169. New York. 1.C. Ito.5 10 10 Du Pont Electronics (Pyralin) Ciba-Geigy (Probimid) Amoco (Ultradel) Toray (Photoneece) (1) Type E = ether. 1998. Nonogaki. as the size of the circuit decreases.5 Conclusions It is clear that the progress in VLSI technology is closely linked to lithographic techniques. 212 . Gazard. 2. NY. The minimum linewidth permitted is already around 0. PI = precyclised polyimide. No doubt these limits will progress and one already speaks of 157 nm projection lithography. Revue Technique Thomson-CSF.8 Examples of polyimide-based photoresists [57] Manufacturer Asahi (Pimel) Trademark G -7610A TL500A IX .C. 6. A. Dubois and M. T. References 1. J. the speed and the power consumption decreases. Microlithography Fundamentals in Semiconductor Devices and Fabrication Technology. 95. 19. Xrays or the 193 nm excimer laser. 1987. Eranian and J. Ueno and T. The requirements placed on photoresists will probably increase in the near future.3 PI 2722 PI 2732 PI 2741 Probimid 343 Probimid 400 Ultradel 7501 UR 3800 UR 5100 Type(1) E E E E E E E PI PI S S Dose (mJ cm-2) 400 400 300 300 <500 80-200 200 700 300 150-250 Shrinkage (%)(2) 48 50 40 50 50 45 40 <9 8 30-40 50-62 Thickness (μm) 10 5 5 5 5 10 10 7. These techniques are dependent on the photochemistry and the resists. Dubois. S. 1974. Revue Technique Thomson-CSF.

inventors. IEEE Transactions on Electron Devices. 11. 12. NY.070. American Chemical Society. Microelectronics. 51. Willson and B.039. 26. Journal of the American Chemical Society.940. 1982. K. 17. S. 10. W. 10. Bowden and E. 217. Ieda. Moritz and G. 151. 3. 13. 1300. 1988.F. 3.. 1980. Grant. van Allan. Semiconductor Lithography: Principle. 14. 213 . NY.D. L’Actualité Chimique. Reichmams and E. Jr. US Patent 4.A. S. Ed. J. DC. 15. Polymer Engineering and Science. 1982. J. inventors. 28. M. Willson and B. 1960. IEEE Electron Device Letters. Wilkins. Pacansky. E.J.G. L. J. Lin. Neugebauer. 1980. 1978. 1982.104.H. 2nd Edition. Heike. USA. N. Eds. Wilkins. USA. 21.W. J. SPIE Optical Engineering Press. 1999. Oldham and E.A. Plenum Press. IBM Journal of Research and Development.C. C. Handbook of Microlithography. 1994.J. Morita. 122. assignee. 1960. 1981.M. Chandross. 86. 1981. 1049. W.G.Photopolymers and Photoresists for Electronics 4. BR Patent 844.. R.. IEEE Electron Device Letters. C. M. 2552. International Business Machines Corporation. King in VSLI Electronics Microstructure Science. Lin. Thompson.A. Academic Press. Journal of the Electrochemical Society. C.G. Tamano.J. Ed. N. 43. USA. 23.J. B. Bellingham. Jain. 1980. 53. 243. 1371. Chapter 2. Practices and Materials. 2. Willson. 20. 1971.W. New York. 16. Washington. Clecak. K. 3. 8. Jain. 3938. Introduction to Microlithography. US Patent 2. Journal of Applied Physics. 1. 19. Paal. 11.G. Journal of the Electrochemical Society. Division of Organic Coatings and Plastics Chemistry Preprints. K. 6. C. Sagura and J. Willson and M. USA. Twieg and C. Clark. 129. Moreau. P. Micromachining and Microfabrication.853. 20.G. Volume 1. 1997. Bowden.J..G. 11. W. 18. 7. New York. 1980. H. Hatori and M. 5. Rai-Choudhury. Dubois. 7. 9. WA. Einspruch. Chandross.G. Reichmanis and C. 11. 1975. E.

B. 34. Applied Polymer Symposia. Iwayanagi. 1982. Lai and L. 1635. Rebek in Radiation Curing in Polymer Science and Technology.369. 185. 279. Journal of the Electrochemical Society.R. Honma and G. Journal of the Electrochemical Society. Ltd. Yokota. Ellenville. MO. Shepherd. S. Kogure. Mid-Hudson Section. Sugawara. K. Elsevier.. Imamura and K. 984. Matsuzawa.Handbook of Polymers in Electronics 22. Doerris. 1304. 1306. Roberts. M. 87. St. 31.H. J. K. 33. Kanai. 124. Processes and Materials. Imamura and S. Iwayanagi. 1981.T. 126. Volume 2. K. Proceedings of the 10th International Symposium on Electron and Ion Beam Science and Technology. Journal of the American Chemical Society. 23. IEEE Transactions on Electron Devices. S. T. 37. inventors.D. Louis. Saeki and M. 23. 1981. 1980) 30. Hacker. A. 1977. Fouassier and J. S. Yamamoto and W. Kohashi. New York. T. H. Matsushita Electrical Co. Matsuda. Journal of the Electrochemical Society. T. Thompson. Kohashi and S. 680. 82-83. 1973. J. Kakuchi. USA. 359. Sugawara.R. N. Tokyo. 1980. Sugarawa. USA. Division of Organic Coatings and Plastics Chemistry Preprints. S. 1. 37. Harada. 1983. M. presented at the 9th International Conference on Electron and Ion Beam Science and Technology. S. 33. Bowden.J. Tada. 1981.F. Nagamatsu.357. 214 . 1979. 35. Japan. 25. NY. assignee. Kilichowski and T. T. Sugegawa. 1982. (Part of the Electrochemical Society Spring Meeting. Chapter 9. O. 2. K. S. Nakane. Tsuchiya. S. 28. 776. 5. S. 21. T. US Patent 4. 1979. 43. 128. 32. 24. M. 48. 1975. Japanese Journal of Applied Physics. T. M. 9. 1977. 72. Bowden and L. Pampalone. E. assignee. Solid State Technology. H. Murase and K. 36. 1648. Extended Abstract. Journal of the Electrochemical Society.J. Douta and H. 27. 1974. Nonogaki. L. Proceedings of the 17th Symposium on Semiconductor and Integrated Circuit Technology. Nonogaki. Proceedings of the Regional Technical Conference on Photopolymers: Principles. S. 22.M. Kohda. Kakuchi. K. 2759. Fahrenholtz and E. Matsuyama. Miyoshi. RCA Corporation. 36. 1982. Yanazawa. 281. US Patent 4. NY. 28. inventors. M. 35. Thompson. SPE. 1993.F. USA. 127. 26. 2. 1979.

L. Monta. 4. Eranian. J. SPE. 1975. Shaw. Kaimoto. M. Kaimoto. Allen. 1979.D. Journal of Vacuum Science and Technology. Simpson. Imamura. 1998. Takechi. L659. Choong and F. Proceedings of the 1st International Polymer Symposium of the Polymer Society of Japan. J. 19. G. 42. Kahn. A.P. B9.Photopolymers and Photoresists for Electronics 38. 47. A. 39. Kogure. R. Abe. Mid-Hudson Section. USA. 215 . Paraszczak. 40. Hanser.S. Shaw. Takechi and N. Proceedings of the Regional Technical Conference on Photopolymers: Principles. 1672. M. Processes and Materials. Liutkus and E. 1981. Abe. Monta and O. Lausanne. Y. 1982. 1.J. Chemistry of Materials. Die Makromolekulare ChemieMacromolecular Symposia. Eranian. J. F. Y. Nozaki. Journal of the Electrochemical Society. Ellenville. Journal of Vacuum Science and Technology.D. 51. FR Patent 7. Thomson CSF. 1280. Proceedings of the Regional Technical Conference on Photopolymers: Principles. Germany. Kogure. 126. 24. Doerries. 41. 1976. Heilman. Bernard and J.615. M. 66. 285. Gazard. Fundamentals and Applications. Tanaka. SPE.D. 3357. Hatzakis. Switzerland. J. Thompson. Preprints from Microcircuit Engineering. 1492.. 6. Duchesne. Barre and C. 1995.D. Tawaka. Japanese Journal of Applied Physics. H. Takahashi. J. M. 1992. inventors. Photopolymerisation and Photocuring. 48. A.D.520. Yau and E.Y. Dubois. T. K. 1994. Fouassier. Mid-Hudson Section.M. assignee.F. Feit. 386. Wallraff. 6. 46. M. Ballantyne and E.C. 50. M. 12.N. Tamamura and O. 1984.E. Ed. Taylor. 10. Photoinitiation.M.F. Ellenville. A. USA. S. Processes and Materials. NY. F. Babich. L. 45. Paraszczak and J. S. 1982. Hatzakis.L.M. 1991. and N. 1989. M. 22. L. Munich. 41. Proceedings of the SPIE. NY. 1121. 10. Willenbrock.P. J. Hinsberg and L. 1703. K. 49. 1983. Nozaki. G. Journal of Vacuum Science and Technology. S. 63. W. Feather and W. 44. Thompson. 355. 43. M.

Polymers for Advanced Technologies. Hinsberg. Watanabe.M. K. 1993. K. Yoda and H. T. 28 November 1999. Nozaki.M. 788. 60. K. Elsevier. W. 2692. Shimokawa. Journal of Macromolecular Science A. Sasago. 21. Wilson. 3. Dubois and J. 1996. J. Hanyu.Yano. A. 9. 1998. 1996. K. Mochizuki. Sillion. 59. 38. M. 1995.C. 56. E1855. Polymer Preprints. J. J.Handbook of Polymers in Electronics 52. 1641. Yamacka. Patterson. N. 11. 216 . Sato. Eds. Yamashita.. N. Techniques de l’Ingénieur. Rubner. Omote.J. K. 425. 57.C. Yano and I. Hiramoto. Dubois and G. S. S. H. 55. 3333. U. 464. A. H. T. Takechi. S. K. Byers and C. E. 58. 4. 1989.G. Nomura. Journal of Photopolymer Science and Technology. Kotachi. T. Bureau. Leuschner and R. Koseki and T. Mizuguchi. Abadie and B. 475.E. 1993. 509. Okoroanyanwu. 53. Ahne. Nagano. Materials Research Society Fall Meeting Tutorial Symposium. S. Kotachi. 54. 1984. 9. Rabilloud. Ono and T. 217. M. 1991. Endo. H. Cho. Journal of Photopolymer Science and Technology. M. Proceedings of the 2nd European Technical Symposium on Polyimides (STEPI). J. Takahashi. Hanyu. R. 1996. Nozaki. Journal of Vacuum Science and Technology B. 61. Takechi and I. Proceedings of the SPIE. Japan.

This prominent position results from the latest developments in the field that have produced a series of new polymers with exceptional electric properties. electric vehicles (EV). The growing market for portable electronic products. and the stringent environmental necessity for zero emission vehicles. 8]. the supercapacitor provides the peak needs for the vehicle acceleration while the battery assures its longrange running. to assure well-balanced vehicle operation. novel-design. The ionic polymers are widely studied as electrolytes for the development of high performance fuel cells and of high energy density batteries. The electronic polymers may find use as electrodes in advanced-design devices.. with particular focus on lithium batteries. In this combined action. e. has motivated research on the development of electrochemical power sources characterised by high energy density. An important step forward in this technology is the replacement of the liquid electrolyte with an ionic membrane and. These high power devices are of increasing importance in the EV technology designed as a support to the energy power sources.g. high energy density batteries are in increasing demand. long cyclability. Another important innovation in the field is the development of redox supercapacitors [7. the so-called lithium-ion batteries [1-6] that are now produced at a rate of a million units per month for the consumer electronics market. namely the electronically and the ionically conducting polymers.1 Introduction Conductive polymers are a class of materials that play a key role in the modern technology for energy storage and conversion. Indeed. Depending on the nature of the electric carriers. A recent breakthrough has been the commercialisation of rechargeable lithium batteries. such as the batteries or the fuel cells. This is an interesting concept since it provides the prospect of a favourable combination of 217 . of the common inorganic-type electrode materials with advanced electronically conducting polymers. in order to produce novel devices having a full polymeric configuration. reliability and safety.7 Polymer Batteries for Electronics B. Both classes of materials are of interest in the energy area. Most of the lithium-ion battery and supercapacitor research and development projects are focused on the fabrication of prototypes using liquid electrolytes. these polymers can be broadly divided into two classes. eventually. such as high-energy batteries and super capacitors. Scrosati 7.

After this. are reviewed. where X is preferably a large anion [9-12]. such as batteries and fuel cells. which are designed as innovative electrodes.. with a lithium salt LiX. the properties and the application potential of the electronically conducting membranes. Indeed.Handbook of Polymers in Electronics the high energy and long life typical of lithium or lithium-ion cells with the reliability and easy manufacturing typical of all-polymer structures.counteranions. A pictorial model of this structural sequence is shown in Figure 7. the first types of lithium polymer electrolytes to be considered for battery applications were those formed by blending high molecular weight poly(ethylene oxide) (PEO). on membranes capable of assuring simple yet efficient structures to power sources mainly directed to EV applications. 218 . i. With respect to batteries.1.2. 7.e. Accordingly. The PEO-LiX membranes are typically prepared by casting an acetonitrile solution of the two components or by directly hot-pressing their intimate mixture.. i. the development of polymer electrolytes has been mainly confined to lithium ion conducting membranes. The polar oxygen atoms in the sequential oxyethylene groups of the PEO chains coordinate the Li+ cations.e. which are designed as electrolyte separators. Some recent advances in the R&D of these two classes of polymer electrolytes will be discussed in the following sections.1 Lithium Polymer Electrolytes and Lithium Batteries Historically. membranes compatible with the electrochemical reactions driving high-energy lithium batteries. 1316] and thus only their essential properties will be briefly recalled. The practical exploitation of this concept requires the availability of polymer membranes having ionic conductivity approaching those of the conventional liquid solutions and of polymer films having charge storage capabilities approaching those of the conventional electrode materials.2 Ionically Conducting Polymers These polymers have been studied and developed in view of their application as electrolyte separators in energy conversion and storage devices. Accordingly. these materials have been generally termed ‘polymer electrolytes’. This chapter attempts to describe the various classes of polymers presently under investigation to meet these requirements. these are the batteries in continuous commercial evolution as ideal power sources for the consumer electronics market. 7. are first discussed. Various books and extensive review articles have been published on these polymer electrolytes [5. Modern fuel cell technology has relied on polymer electrolytes with proton transport. the structure of the PEO-LiX complexes may be broadly discussed as a sequence of polymer chains coiled around the lithium ions while the anions are more loosely coordinated [14]. The ionically conducting polymer membranes. separating them from their X.

increases. expressed as the ratio between the oxygen atoms in PEO and of the lithium ions in LiX.1). when the system is in its crystalline state. This is shown by Figure 7. It may be clearly noticed that at ambient temperature.1 Schematic structural arrangements of the PEO chains coiling around Li+ cations This oversimplified picture progressively diverges from reality depending upon the relative concentration of the two components. As for all conductors. The number of the Li+ carriers increases as the LiX concentration increases. the conductivity of the PEO-LiX polymer electrolytes depends on the number of the ionic carriers and on their mobility. at the crystalline to amorphous PEO transition. which on average occurs at temperatures above 70 °C. but their mobility is greatly depressed by the progressive occurrence of ion-ion interaction which may even lead to large ion cluster formation [14].. i.2..e. high conductivity and fast Li+ ion transport are restricted to the amorphous state of the PEO component.Polymer Batteries for Electronics Figure 7. As the concentration of the LiX. Due to their particular structural position (Figure 7. Thus. the Li+ ions can be released to transport the current only upon unfolding of the coordinating PEO chains. the overall structure becomes more and more complicated due to ion-ion and association phenomena [17]. at around 70 °C. which illustrates the phase diagram and the ionic conductivity Arrhenius plot of a typical electrolyte in the PEO-LiClO4 system. the conductivity increases by 219 . However.e. the conductivity is very low. in the 10-8-10-7 S cm-1 range. i.

2 Phase diagram and conductivity Arrhenius plot of the PEO-LiClO4 polymer electrolyte. 20] is given in Figure 7. This implies that the use of the PEO-LiX electrolytes is restricted to batteries for which a relatively high temperature of operation does not represent a major problem. while the electrons travel through the external circuit to reach the cathode and modify its electronic density of states [23]. produced at the Li metal anode. around 10-3 S cm-1) at 100 °C. Indeed. various R&D projects aimed at the production of PEO-based.Handbook of Polymers in Electronics Figure 7..g. The charging process is the exact opposite and thus the overall process may be written as shown in Equation 7. A schematic diagram of an electrochemical process of the battery reported in the literature [2. which provides channels for the reversible insertion-deinsertion of lithium ions [21-23]. These batteries typically use a lithium metal anode and a Li-intercalation cathode. several orders of magnitude to reach values of practical interest (i.e. V2O5. LiCoO2. batteries designed for EV traction. xLi + AyBz ⇔ LixAyBz (7.. x is percent fraction of LiClO4. LiMn2O4) structure. It is possible to name this intercalation cathode by the general AyBz notation. the Li+ ions.g. a layered (e. Upon discharge..3.g. V6O13. e... The latter may be basically described as a compound with an ‘open structure’. TiS2.e. EV lithium batteries are in progress worldwide [18-20]. i.) or a tunnel (e. travel across the electrolyte to reach the AyBz cathode and are inserted into its structure.1.1) 220 .

Accordingly.4. crosslinked polymer networks and comb-shaped polymers having short oligooxyethylene chains attached to the polymer 221 . published by Societa Chimica Italiana) The open circuit voltage of this battery is associated with the difference in the Fermi levels of the two electrodes. Although these projects are very relevant..g. the high temperature operation of the batteries obviously limits their practical output. La Chimica e l’Industria. the use of modified PEO polymer architectures to achieve low crystallinity at room temperature. is given in Figure 7. many studies have been carried out with the goal of improving the conductivity of the PEO-based polymer electrolytes at ambient temperature. Scrosati. the discharge voltage decreases upon increasing lithium intercalation level (x in Equation 7. 1997. where AyBz is TiS2. Accordingly.1.3 Schematic diagram of the Li-AyBz lithium battery (Reproduced with permission from B. These include block copolymers. if the overall process does not induce phase changes in the host AyBz cathode.1). 5. A typical example.Polymer Batteries for Electronics Figure 7. e. Various approaches have been considered. 464. Some selected examples of R&D projects presently in progress for EV lithium polymer batteries [24-26] are listed in Table 7.

backbone [14. these modified PEO electrolytes (in particular the ones with added plasticiser).. EF = Fermi level. Derived from [23].g.4 The Li/TiS2 cell. although reaching high levels of conductivity. propylene carbonate (PC) or ethylene carbonate (EC) [30. Open circuit voltage (a) and voltage discharge profile (b) upon development of the xLi + TiS2 ⇒ LixTiS2 discharge process. Other approaches have considered the addition of plasticisers. DOS = density of states.Handbook of Polymers in Electronics Figure 7. Eg = band gap. 31] or low molecular weight ethylene glycols [32]. e. 222 . 27-29]. such as organic liquids. However.

the ceramic additive.e. to our knowledge. lowering the polymer chain reorganisation tendency and promoting 223 . It may be seen that the related Arrhenius plot does not break around 70 °C. It has been proposed [44] that the Lewis acid character of the added ceramic may compete with that of the lithium cations for the formation of complexes with the PEO chains. namely of solid additives which would promote amorphicity at ambient temperature without affecting the mechanical and the interfacial properties of the electrolyte. above 70 °C). due to its large surface area.Polymer Batteries for Electronics Table 7. Thus. 33. ceramic-free electrolytes. in the PEO-LiX matrix [3541]. Therefore. Al2O3 and SiO2. such as TiO2. A result that approaches this ideal condition has been obtained by dispersing selected ceramic powders.. Indeed. compared to the 10-7 S cm1 of the standard. as typically expected for PEO-based electrolyes. the ceramics may act as crosslinking centres for the PEO segments. reactivity toward the lithium metal electrode [20. This outstanding effect is explained by assuming that. 42. no practical lithium battery using a plasticiser-added polymer electrolyte has so far reached large-scale production. 43]. at the nanoscale particle size. 34] that may rule them out from practical applications. prevents local PEO chain reorganisation with the result of freezing a high degree of disorder which favours the Li+ ion transport [38. once the composite electrolyte is annealed at temperatures higher than the PEO crystalline to amorphous transition (i. It clearly suggests that the added ceramics prevent PEO crystallisation. The conductivity behaviour of a selected example of these ‘nanocomposite’ polymer electrolytes is shown in Figure 7. particularly.1 Some examples of R&D projects for the lithium polymer batteries for EV application Project 3M-Hydroquebec-Argonne (North America) Bolloré-EDF-CEA/CEREM (France) ENEA-ARCOTRONICS Universities (Italy) System Li/PEO-LiX/VOx Li/PEO-LiX/VOx Li/PEO-LiXcomposite/LiMn2O4 Status EV module prototypes Prototypes Demonstration prototypes Italian Government Support USABC USABC: United States Battery Consortium suffer from serious drawbacks such as the loss of mechanical stability and.5. with a resulting enhancement in conductivity which at room temperature may reach values of the order of 10-5 S cm-1. the ideal solution in this field would be the use of ‘solid plasticisers’.

1).e. w/o = weight percentage.6. 53]. Peled and co-workers [54-56] have reported another interesting battery application of the PEO-based composite electrolytes in a cell of the following structure: Li/(PEO)20LiI-EC-Al2O3/FeS2 224 . In addition.Handbook of Polymers in Electronics Figure 7. the lithium manganese spinel operating in its medium (3V vs. The cathode was LiMn2O4.. The fabrication and test of prototypes based on the preferred composite electrolyte (a PEO-LiCF3SO3 system with dispersed γ-LiAlO2 ceramic powders) has been demonstrated (Table 7. i. all these properties making them suitable for use as safe and efficient separators in rechargeable lithium batteries [51]. Therefore. Li+ conducting pathways at the ceramic surface [44-46]. The voltage profile of this battery is shown in Figure 7. Li) voltage range [52. Long cycle life and an energy density of the order of 110 Wh kg-1 are expected for this battery [26].5 Conductivity Arrhenius plots of ceramic-free and composite PEO-based. polymer electrolytes. according to this model. the all-solid configuration (no addition of liquids) gives to these nanocomposite electrolytes a high compatibility with the lithium metal electrode [47-50]. the structural modifications at microscopic levels promote consistent enhancement in the transport properties of the electrolyte.

(iii) the short-time heating of the slurry at around 90-100 °C for promoting complete homogenisation. the gel membranes cannot be classified as ‘true’ polymer electrolytes.7. 4 Li + FeS2 ⇔ Fe + 2Li2S (7. (ii) the addition of the polymer component and its dispersion in the solution. e. Strictly speaking. 5759]. polyacrylonitrile (PAN).. but rather as hybrid systems where a liquid phase is contained within a polymer matrix. The cell operates at 135 °C on the basis of the overall process shown in Equation 7. The gelification procedure may involve a sequence of steps including: (i) the dissolution of the lithium salt in the given organic solvent mixture. For instance. Derived from [26]. The most successful result has been obtained with the development of electrolyte membranes formed by trapping liquid solutions (e. casting and gelification.g.g. The immobilisation procedure varies from case to case and includes UV crosslinking. and (iv) the cooling of the resulting solution to room temperature to promote gelification [60]. the latter being the most commonly adopted.6 Voltage profile of a typical charge-discharge cycle of a Li /PEO-LiCF3SO3 + γLiAlO2 / LiMn2O4 polymer battery at 94 °C and at C/10 rate.2.2) The overall process is associated with a theoretical energy density of 800 Wh kg-1 and a voltage slope between 2.Polymer Batteries for Electronics Figure 7. PMMA or polyvinylidene fluoride (PVdF) matrices [20.. ΔV is the charge (upper curve) and discharge (lower curve) voltage.8 V. The need to extend the use of polymer electrolytes to devices capable of operating at ambient and sub-ambient temperatures has motivated the search for materials capable of offering values of conductivity even higher than those of the PEO-LiX composites. 225 . These gel-type membranes will be hereafter simply indicated by listing their components in sequence. will be here indicated as LiPF6-EC-DMC-PAN.5 V and 1. solutions of a lithium salt in organic solvent mixtures) in a polymer. A schematic view of this structure is represented in Figure 7. the gel electrolyte formed by immobilising an ethylene carbonate-dimethyl carbonate lithium hexafluorophosfate solution in PAN.

7 Schematic representation of gel-type polymer electrolyte configuration 226 .Handbook of Polymers in Electronics Figure 7.

indicating that the membrane does not degrade by crystallisation or phase separation phenomena either upon thermal or time excursions. Some examples of these membranes with their composition and their electrochemical properties are listed in Table 7. 68-74]. is not sufficient to make a given electrolyte suitable for battery applications. approaching 10-2 S cm-1 and remains stable for many days. These structural differences may be of importance when a selection has to be made in view of battery application. the PAN-based membranes. Thus. In general. 63] and Raman [64-66] spectroscopy studies show that some interactions do occur between the polymer backbone and the electrolyte solution. which shows the Arrhenius plots of some selected examples.e.. while the latter can be regarded as hybrid systems where the liquid solutions are imbedded in a ‘passive’ host polymer. Recent papers reporting NMR [62. The trend shows that the conductivity is quite high.2 [72]. interest in these materials has increased recently with the development and the characterisation of many new types of membranes having different properties [59. For instance. In general. having characteristics which approach those of a ‘true’ polymer electrolyte entity. This test can be carried out by running sweep voltametry on cells using the given membrane as electrolyte. and Figure 7.8. Under 227 . Clearly. are expected to be more stable than the PMMA-based counterparts and thus to offer a higher reliability as practical battery separators. This can be seen in Figure 7. there has been some discussion as to whether these gel electrolytes are indeed simple two-phase materials where the polymer is a passive component acting as a rigid framework for regions of liquid solutions or whether they are integrated systems where the polymer provides the stability of the gel network down to the immediate vicinity of the Li+ ions [61]. Additionally.5 which compares the conductivity of gels with that of PEO-based membranes. the chemical and electrochemical stability are key parameters. is shown in Figure 7. Feullade and Perche [67] originally introduced gel-type electrolytes. a high ionic conductivity. to an extent that depends upon the nature of the two components. the storage temperature. approaching that of liquid solutions. a ‘blocking’ (i. not reversible to the membrane’s mobile ion) working electrode and a third reference electrode. has been shown. The time evolution of the conductivity of a LiPF6-EC-PC-PAN electrolyte obtained at 25 °C.9 [74]. However. these gel-type electrolytes have quite promising properties in terms of conductivity.Polymer Batteries for Electronics However. whereas in those using the PMMA matrix the interaction is weak [65]. the electrochemical stability of an electrolyte is typically established by determining its breakdown voltage. clear evidence of coordination between the polymer backbone and both the solvated ions and the solvent molecules. while obviously an important feature. the former are systems characterised by an ‘active’ polymer experiencing strong interactions with the solutions. in the case of electrolytes using a PAN matrix. However.

5-56.1 x 10 -3 -3 LiClO4-EC-PC-PAN LiClO4-EC-PC-PAN LiClO4-EC-DMC -PAN LiClO4-EC-DEC-PAN LiClO4-γBL-PAN LiAsF6-EC-PC-PAN LiAsF6-γBL-PAN LiPF6-γBL-PAN LiPF6-EC-γBL-PAN LiPF6-EC-DMC-PAN LiN(SO2CF3)2-EC-PC-PAN LiN(SO2CF3)2-EC-γBL-PAN LiClO4-EC-PC-PMMA LiAsF6-EC-PC-PMMA LiN(SO2CF3)2-EC-PC-PMMA LiN(SO2CF3)2-EC-DMC-PMMA LiC(CF3SO2)3-EC-DBP-PVdF LiC(CF3SO2)3-EC-DBP-PVdF(C3F6) LiC(CF3SO2)3-EC-PC-PVdF(CTFE) 8.0 4.0* 4.0-16.0* 4.0-50.0-30.0-30.9 4.5-23.0-20.0* 4.6 4.0-62.0* 4.5-23.3 4.0-33.0* 3.017 x 10 0.5-46.0-21.5 x 10-3 4.0-20.035 x 10 0.5-56.1 x 10 -3 4.0-16.5-19.0* 4.5-79.5-19.0* 4.0* 4.8-40.2 x 10 -3 -3 1.0 x 10 2.6 4.0-30.9 x 10 -3 -3 4.0-16.0* 4.8 x 10-3 0.0-30.8 -3 -3 3.0-16.1 4.6 4.5-46.0-38.2-42.1 4.4 4.5-30.5-79.9 5.5-30.5-23.5-23.0 4.0* 5.5-19.0-16.8 5.5-16.8 4.1 x 10-3 0.0* 4.5-36.6 x 10-3 0.0* 4.1 x 10 4.7 x 10-3 0.0* 4.0* 1.5-56.5-46.7 4.0-25.5-36.1 x 10-3 1.0-23.0* 3.5-79.5-53.Handbook of Polymers in Electronics Table 7.5-56.0* 4.5-23.5-19.0-16.5-16.2 Composition and electrochemical properties at 25 °C of some selected examples of gel-type polymer electrolytes (average thickness = 100 mm) Electrolyte membrane Molar composition Conductivity Anodic (S cm-1) breakdown voltage vs.0 x 10-3 2.5-56.5-16.0-30. Li+/Lio (V) 1.6 5.0* 5.0* 4.0* 4.5-23.0-14.8 4.0-16.9 x 10 4.7 x 10 1.8 x 10 -3 -3 0.5-56.6 (* = this value is referred to monomer) DEC = diethylene carbonate γ BL = γ -butyrolactone CTFE = chlorotrifluoroethylene DBP = dibutylphthalate 228 .4 x 10-3 5.

9 Time evolution of the conductivity of the LiPF6-EC-PC-PAN electrolyte at 25 °C 229 . The plot of a typical liquid solution is also reported for comparison purposes. Figure 7.Polymer Batteries for Electronics Figure 7.8 Conductivity Arrhenius plots of various gel-type electrolytes.

the high conductivity of the gel electrolytes may be exploited in an effective way by directing them to the development of new-design.5 V s-1.10 Sweep voltammetry of a Ni electrode in a LiPF6-EC-PC-PAN electrolyte cell at 25 °C. Basically. In practice. high-energy lithium batteries.10. their use may be limited by the reactivity towards the lithium electrodes induced by the high content of the liquid component. Indeed. the gel-type electrolytes. Li counter electrode. the test has been run by using a Ni blocking electrode and a Li reference electrode. such as a carbon or graphite [75]. One may then conclude that. In the case of the gel-type membranes under discussion here. these conditions. severe passivation phenomenon occurs when the lithium metal electrode is kept in contact with the gel electrolytes [60. Scan rate: 0. these batteries operate on the cyclic transport of lithium ions from one lithium- 230 . this being high enough to allow the safe use of the electrolyte membrane with a large selection of electrode couples. the voltage at which the current starts to flow through the cell may be assumed as the decomposition of the electrolyte. This confirms the general rule that if from one side the wet-like configuration is essential to confer high conductivity to a given polymer electrolyte. Results obtained for the LiPF6-EC-PC-PAN electrolyte are shown in Figure 7. These are the so-called ‘rocking chair’ or. have electrochemical properties that in principle make them suitable for application in versatile.Handbook of Polymers in Electronics Figure 7. 69]. from the other it unavoidably affects its interfacial stability with the lithium metal electrode. The current onset is detected around 4. more commonly ‘lithium-ion’ batteries [76]. plastic-like batteries where the lithium metal anode is replaced by a lithium-accepting compound. Li. On the other hand.3 V vs. and the PAN-based ones in particular.

11). 5. prevalently by Japanese manufacturing companies [20] and directed to the consumer electronics market where they have now assumed a prominent position [2]. Scrosati. the three contacted layers are coiled one on top of the other to obtain a spirally wound geometry having a high surface area. 6.. 1997.11 Schematic representation of a cylindrical lithium-ion battery (Reproduced with permission from B. usually aluminum) foil. C). alternatively. This assembly is then housed in a suitable container which. 20] (e.g. by layering in sequence a thin layer of the carbon anode (backed on a metal. 465. La Chimica e l’Industria. according to the general overall process shown in Equation 7. LiCoO2 or. In a typical cylindrical design (Figure 7. conductive carbon and binder) cathode (backed on a metal. usually copper) foil collector. is hermetically sealed to prevent either leakage or Figure 7. after tapping with the liquid electrolyte.3 6C + LiCoO2 ⇔ LixC6 + Li1-xCoO2 (7.. LiNiyCo1-yO2 or LiMn2O4) to a lithium-poor anode [1. These commercial batteries are commonly prepared in the so-called ‘bobbin-type’ configuration.g.3) These lithium-ion batteries are quite effective and are presently produced at a rate of several millions of units per months. published by Societa Chimica Italiana) 231 .Polymer Batteries for Electronics rich cathode (e. a microporous separator felt and the composite (blend of active material.

the LiPF6-EC-DMC solution) throughout the separator membrane and the electrode films [79]. This membrane is capable of absorbing large quantities of liquid electrolytes and this feature has been exploited for a battery fabrication process which initially involves the lamination of three battery components. the anode film.g.e. liquidphilic membrane follows this first step.g. i. commercially available lithium-ion batteries use a liquid electrolyte. An approach in this direction is based on the use of an elasticised electrolyte membrane separator formed by a copolymer of vinylidene fluoride and hexafluoropropylene [77.. This has been carried out by examining the characteristics of the lithium intercalation-deintercalation processes in the electrode materials using cells based on the given polymer as the electrolyte and lithium metal as the counter electrode. 232 . the carbonaceous anode and the lithium metal oxide cathode. As an example.. they have a configuration which in principle allows a single lamination process for the fabrication of the lithium-ion battery. The feasibility of the gel electrolytes for lithium-ion batteries development has been tested by first examining their compatibility with appropriate electrode materials. Finally.g. This is expected to be an important technological progress because it provides the prospect of a favourable combination of the high energy and long life typical of the lithium-ion concept. Therefore. Alternative routes to obtain lithium-ion plastic batteries have considered the use of PANbased gel-type polymer electrolytes as separators. The response follows Equation 7.12.e.4. Accordingly.7).. contain in their structure the active liquid electrolyte (Figure 7. the voltage response of a graphite electrode cycled in a LiClO4-ECDMC-PAN electrolyte cell is shown in Figure 7. One of the requirements for a successful result is the availability of polymer electrolyte membranes having electrical and chemical properties comparable with those of the common liquid electrolytes.Handbook of Polymers in Electronics contact with the external environment. the membrane soaked with a low vapour pressure plasticiser and the cathode film.. i. A second process in which the plasticiser is eliminated to precondition the separator into a highly porous.e. This procedure is commonly used to produce a series of different geometries that includes prismatic as well as cylindrical cases. activation is accomplished by spreading a suitable lithiumion liquid electrolyte solution (e. EC-DMC). The next important step in this technology is the replacement of the fibre separator embedded with the liquid electrolyte with a polymer membrane that can act both as the separator and the electrolyte. a process that avoids intermediate liquid extraction-soaking activation steps.. LiPF6) in an organic solvent mixture (e. These electrolyte membranes. i. many attempts to reach this goal are presently underway.. The most common. generally formed by a solution of a lithium salt (e. although macroscopically solid. 78]. with the reliability and diversified design that the plastic configuration may offer.

namely a voltage profile which. As in the case of the graphite anode. again 233 . Cycling rate: C/4. which have demonstrated that the formal excess capacity during the initial cycles is due to the side reactions involving the decomposition of the electrolyte with the formation of a passivation layer on the graphite electrode surface [82. Lithium counter electrode. This is also expected on the basis of the results obtained in liquid electrolytes. Li (Figure 7. thus allowing the continuation of the electrochemical intercalation process down to very low voltage levels. around 50 mV vs. during the intercalation process. the electrochemical response of the cathodes can also be evaluated by following the lithium intercalation-deintercalation processes. xLi+ + 6C ⇔ LixC6 (7. the occurrence of this passivation layer. is essential for assuring the proper cyclability to the graphite electrode [1].12) and with a reversible capacity which cycles around 300 mAh g-1. respectively. although with an apparent loss in capacity. It may be noted that. when the graphite anode is coupled with a lithium metal oxide cathode. 81].Polymer Batteries for Electronics Figure 7. often called the solid electrolyte interface (SEI) [84] prevents the decomposition of the electrolyte. 83]. in contrast with the case of the lithium metal electrode.e. which is electronically insulating but lithium ion conducting. lithium deintercalation process. i. decreases along a series of distinguishable plateaus corresponding to the progressively occupied staging graphite phases [80..4) It has been seen that the response approaches that observed in liquid electrolyte cells. The layer.12 Typical voltage response of the Li intercalation-deintercalation process of a graphite electrode in a LiClO4-EC-DMC-PAN electrolyte cell. Temperature: 25 °C. A similar trend is reproduced upon the reverse. These two features are important to maintain high battery voltage and a long cyclability.

13 demonstrates that the voltage profile and the cycling capacity (about 130 mAh g-1) match those expected for these cathode materials in liquid electrolyte cells.13.6. Lithium counter electrode. such as Cr. 85-87].5. Once the compatibility of the gel-type electrolyte with both anode and cathode materials is ascertained. using cells with a gel electrolyte and a lithium metal counter electrode. A few examples of these prototypes have been reported at the laboratory level scale. One is provided by a battery of the type C/ LiClO4-EC-PC-PAN/LiCryMn2-yO4. the data collected to promote and evaluate the process as shown in Equation 7. The results obtained in the case of a lithium manganese spinel cathode cycled in a LiClO4-EC-DMC-PAN electrolyte cell are reported in Figure 7. 81]. The use of a metal-doped manganese spinel is common in the lithium-ion technology since it has been demonstrated that a partial substitution of Mn (III) with M (III) metals. Cycling rate: C/4. conferring to the cathode a good capacity retention upon cycling [53. 234 . one can proceed with the combination of the two for the fabrication of polymer-based lithium-ion battery prototypes.13 Typical voltage response of the Li intercalation-deintercalation process of a LiCryMn(2-y)O4 electrode in a LiClO4-EC-DMC-PAN electrolyte cell. may consistently stabilise the spinel structure. The overall process of this battery is shown in Equation 7. LiCryMn2-yO4 ⇔ Li1-xCryMn2-yO4 + xLi+ + xe (7. a Cr-added spinel has been used in this test. This battery was fabricated and tested under a coin-type cell configuration [80. Temperature: 25 °C. The trend seen in Figure 7.5) Instead of the stoichiometric LiMn2O4.Handbook of Polymers in Electronics Figure 7.

+ Li+ ⇒ Li2Mn2O4 (7.8.7 at the anode. 90]. LiMn2O4 + e. the first charging process of the battery may be written as shown in Equation 7.8) (7.6) A typical charge-discharge cycle is shown in Figure 7. KC8 ⇒ K+ + e. Cycling rate: C/10.14. which on subsequent cycles performs with fast kinetics of its lithium intercalation-deintercalation process [89. Accordingly. and confirms the feasibility of the PAN-based gel electrolytes as separators in lithium-ion batteries by showing that the cell can indeed be cycled with a good capacity delivery. 6C + LiCryMn2-yO4 ⇔ LixC6+ Li1-xCryMn2-yO4 (7. The discharge 235 . Another lithium-ion polymer cell recently tested as a laboratory-scale prototype [88] has the configuration KC8/LiClO4-EC-PC-PAN/LiMn2O4. Upon anodic polarisation this electrode irreversibly deintercalates potassium resulting in a graphite-like compound.14 Typical voltage profile of the charge-discharge cycles of the Li/LiClO4-EC-DMC-PAN/LiCryMn(2-y)O4 polymer battery at 25 °C.+ 8C The reaction at the cathode is shown in Equation 7.Polymer Batteries for Electronics Figure 7. In this case a potassium-graphite (KC8) electrode has been used as the carbonaceous anode material.7) The charge balance in the electrolyte is assured since the amount of Li+ intercalated in Li2MnO4 is compensated by the amount of K+ deintercalated from KC8.

11) The lithium oxide. the reversible release and uptake of lithium shown in Equation 7. Convertible oxides.2O2 electrodic couple [92]. SnO2 + 4Li ⇒ Sn + 2Li2O (7.10 and by a certain tendency to lose capacity upon cycling.8Co0. Sn + 4. and tin oxide in particular.2O2 ⇔ xLi+ + Li1-xNi0. This greatly improves the cyclability of the electrode [94].4Li ⇔ Li4. These processes have been confirmed by the experimental response of the cell [8] which showed a voltage profile developing around the 3V characteristic of the lithiumrich manganese spinel phase [91] and delivered about 80% of the theoretical capacity at 0. tin oxide first undergoes an irreversible reaction shown in Equation 7.11. although the latter issue can be largely controlled. initial irreversible capacity associated with reaction 7. 94].12. Another interesting application of the lithium-ion battery concept has been applied to the SnO2/LiNi0. which reaches values approaching 700 mAh g-1.4Sn (7. This material is presently considered as a valid alternative to the more common LiCoO2 cathode.e. The electrochemical process is similar in both cases. When negatively polarised in a lithium cell.8Co0.8Co0.9) In this system.10. both in terms of cost and environmental compatibility [103. i. according to the typical lithium-ion process shown in Equation 7.10) This results in metallic Sn particles that remain finely dispersed in the Li2O matrix. almost double that offered by the more conventional graphite electrode.2O2 (7. surrounded by the tin particles.9.e. This feature is somewhat contrasted by a large. first proposed as alternative anode materials by the Japanese Fuji Photo Film Company [93.12) 236 . i. are presently the object of considerable attention in the lithium-ion battery community [95-98].1 mA cm-2 cycling rate [88]. the maximum achievable specific capacity is 372 mA g-1 referred to the anode. This produces a favourable geometry and facilitates a subsequent reversible reaction as indicated by the lithium alloying-dealloying process shown in Equation 7.. 104].Handbook of Polymers in Electronics process and all the other cycles involve the cycling of the Li+ ions between the two electrodes. 8C + Li2Mn2O4 ⇔ 4/3LiC6 + Li2/3Mn2O4 (7.. A Ni-Co mixed compound can be used as the cathode. The interest in this electrode lies in its high specific capacity. LiNi0. creates a sufficient amount of free volume to accommodate the mechanical stresses experienced by the metal particles during the course of the process.

Cycling rate: 0.Polymer Batteries for Electronics Considering the reactions of the two electrodes.2O2 polymer battery at 25 °C. The voltage profile of a typical discharge-charge cycle of this cell is shown in Figure 7.15 Typical voltage profile of a charge-discharge cycle of the SnO2 / LiClO4EC-DMC-PAN / LiNi0.25 mA cm-2.8Co0.2O2 (7.2O2 cell may. although with a certain progressive fade.13. under steady conditions. delivering a reversible capacity approaching 300 mAh g-1. LiNi0. the overall process of the SnO2/ LiNi0.2O2 + Sn ⇔ LixSn + Li1-xNi0. along with anode and cathode voltage variations. It may be seen that the SnO2 anode cycles with a trend comparable to that usually obtained in more conventional liquid electrolyte cells [105]. 237 . Figure 7.8Co0. this again being experienced in liquid-electrolyte cells as well.15.8Co0.13) This process has been exploited for running a laboratory prototype polymer lithium-ion cell based on the LiClO4-EC-DMC-PAN electrolyte. be written as shown in Equation 7.8Co0. This capacity level is maintained upon further cycling.

5 V versus Li and is accompanied by very little change in lattice dimension. In this case.PC. which is about 1. i. Li4Ti5O12 + 3Li ⇔ Li7Ti5O12 (7. e.14) This system evolves around 1.16. 109]. An apparent drawback of this cell is its relatively low overall voltage.g. intercalation compound. a material of the Li [Li1/3Ti5/3]O4 family [108. as opposed to the lithium-metal alloy cases discussed above. which stabilises around 2. The difference is in the voltage levels of the two anode materials. has been used as an anode. This important feature has been experimentally confirmed [107] by determining the response of a lithium-ion polymer prototype cell such as Li4Ti5O12/LiPF6 -EC-PC-PAN/LiMn2O4.050 V vs. 1. Figure 7.Handbook of Polymers in Electronics Peramunage and Abraham have recently reported an advanced lithium-ion polymer cell [106.5 V less than that of more conventional lithium-ion systems based on graphite anodes. the absence of structural deformation makes Li4Ti5O12 an almost ‘zero strain’ electrode material characterised by a very good cyclability and by very little capacity fade upon cycling. Some charge-discharge cycles obtained for the cell are shown in Figure 7. Inc.5 V.PAN/ LiMn2O4 polymer battery at 25 °C. (From reference 107.5 V versus Li for Li4Ti5O12 versus the 0.) 238 . Thus.. The lithium intercalationdeintercalation process in this compound is shown in Equation 7. 107].e.. the Li4Ti5O12. Cycling current densities are shown in the figure.14. Li for graphite.16 Voltage profile of a charge-discharge cycles of the Li4Ti5O12/LiPF6-EC. reproduced by permission of the Electrochemical Society.

with even less details of the type of electrode and electrolyte materials used for their products [110]. According to the released information. particularly. This may lead to the conclusion that the evolution of the lithium-ion battery technology will be focused on polymer configurations with an output that is expected to soon experience a substantial share in the electronics market. 239 . such as the Li4Ti5O12 discussed above. the proton conductivity of the known polymer systems still remains below the upper limit of proton conductivity in liquids. The results so far described. with important advantages in terms of the cyclability and safety of the battery. including sensors and. Shipments of lithium-ion polymer electrolyte batteries have also been reported by Ultralife Batteries in the USA [112]. particularly the new generation of cellular phones. it is not possible at this stage to evaluate the effective status of the development of these advanced types of batteries.2 Proton Polymer Electrolytes The research into proton conducting polymer electrolytes has consistently increased in recent years due to the transport characteristics which make them promising for various electrochemical applications of interest for the electronics market. other than proton conductivity. in the future. One can only cite that the Japanese Matsushita Battery Company has announced the completion of the facility for the large-scale production of thin-film lithium-ion polymer batteries [111]. commercial production of lithium-ion polymer batteries [110]. these commercial lithium-ion polymer batteries have characteristics. no information is available on the nature of the polymer electrolyte or on the type of electrodes selected for this development. However. fuel cells [113]. 7. which must be met for any specific application. However. Apparently. have announced similar activity. various battery manufacturer companies worldwide have announced their involvement in the large-scale. are somewhat limited to cases involving laboratory cells. such as reduction in thickness and improvements in safety. This in turn opens new avenues for electrode materials operating within the stability window of the electrolyte. wherein the use of the batteries is directed. this may not be an issue in the near future considering that the trend in electronics circuitry. including Sony Energy Technology and Toshiba. to an even lower range. the constraint of choosing low-voltage anodes. is that the voltage-powering request will be progressively reduced from the initial 4 V to 3 V and. More recently. a Li1+xMn2-xO4 cathode and a polymer electrolyte which has not yet been disclosed. Nevertheless.Polymer Batteries for Electronics However. This may somewhat eliminate the need for high-voltage power sources and thus.2. The major problems arise from the numerous additional requirements. which make them very appealing for the modern consumer electronics markets. the level of released information is very scarce and. these batteries use a graphite anode. although demonstrating the feasibility of the lithium-ion concept in polymer electrolyte batteries. Other Japanese companies.

but also to optimise the environment of the proton. It may be noted that it is not only important to adjust the polymeric host to the requirements of a particular application as described above. higher than 10-3 S cm-1 at ambient temperature) at water contents exceeding 30% wt. This concept has been applied to develop proton conducting polymeric gel or hydrogel membranes [121-123] which reach conductivity values around 10-3 S cm-1 at room temperature and are not destroyed or dissolved even at high humidity levels.. In fact. while the hydrated hydrophilic domains provide high proton conductivity (i. due to the hydrophilic nature of the sulfonic groups attached to the polymer backbone. such as H2SO4 or H3PO4. the inclusion of basic nitrogen groups in branched polyethyleneimine-H2SO4 or imidazole sulfonated polyaromatic membranes is expected to produce an increase in conductivity. the hydrophobic part of this polymer provides a relatively good mechanical stability even in the presence of water. As is well known. The question is whether the procedure successfully used for the fabrication of gel-type. Indeed. the high conductivity (around 10-2 S cm-1) observed at room temperature for the PAAM-H2SO4 electrolyte has been attributed to the protonation capability of the amide groups [118]. Indeed. Recently. many studies have been performed on proton conducting electrolytes based on polar polymers having basic sites.e. Particularly. new. Effectively. In the same way. one may consider that ionic transport in crosslinked swollen polymers containing a low molecular weight polar or ion-chelating additive may indeed occur in the solvent phase and thus. that the gel concept can be extended to the proton conducting systems. proton conducting polymeric gel or hydrogel membranes with conductivity values around 10-3 S cm-1 have been developed in the past [122]. Nafion is somewhat affected by some operational problems and thus. the ionic transport in linear or crosslinked swollen polymers containing a low molecular weight polar or ion-chelating additive mainly occurs in the solvent phase [118. This effect could be attributed to the proton exchange between two amine groups. Accordingly.Handbook of Polymers in Electronics Nafion is presently the material of choice. In this respect. As suggested by Kreuer [119]. these species result in the generation of protonic defects in the non polar gel environment. a new approach aimed at 240 . These sites form compounds with strong acids. 120]. adding protonated and unprotonated solvent species can increase proton transport. In general. the amide group has basicity comparable to that of water and thus it can be protonated at either the oxygen or the nitrogen atoms. lithium conducting polymer electrolytes discussed in the previous paragraph may be successfully extended to other ion conducting systems. because it acts as a good. polybenzimidazole (PBI). In fact. intense research efforts are presently directed to reach this goal. 117]. optimised proton conducting membranes would be highly welcome. polyvinylpyrrolidone (PVP) and polyacrylamide (PAAM) form complexes with inorganic acids [116. chemically inert and stable polymer electrolyte [114]. Although widely used. the conductivity strongly depends upon relative humidity [115]. As is well known.

the melting point of these acid molecules is generally higher than the boiling point of water. These membranes feature as robust electrolyte systems with a thermal stability that extends up to 70-90 °C [124]. while the ring itself is rather non polar. with low contents of protophilic solvents (such as dimethylformamide (DMF). (From reference 124. methylformamide or formamide) into a highly plasticised PMMA matrix [124.Polymer Batteries for Electronics developing proton conducting gel membranes having transport properties not dramatically dependent on the humidity level has been reported [124]. which makes them interesting candidates for supporting high proton conductivity at room temperature. such as PC and EC. 125]. Figure 7. In addition. Here the carboxylic groups are expected to be able to act as proton donors and to show low levels of hydration.17 Conductivity of proton membranes as function of the humidity content.) 241 . Inc. This effect was in part attributed to a specific interaction between the polymer and the non polar fragment of the SA molecule. It is also important to point out that the conductivity values of the membranes were found to be higher than those of the plain liquid solutions. These novel types of proton gel electrolyte membranes have been obtained by incorporating salicylic acid (SA) or benzoic acid in a highly plasticised PMMA matrix. In addition. reproduced by permission of the Electrochemical Society. it was assumed that the presence of DMF induces a more polar environment inside the gel matrix due to their strongly polar amide groups [124]. The synthesis involved the mixing of solutions of organic acids in protophobic solvents. thus enhancing ionic transport.

e.2.Handbook of Polymers in Electronics The effect of the environmental humidity on the conductivity of SA-based PMMA membranes compared with that of a typical Nafion membrane.3 Electronically Conducting Polymers The discovery in the late 1970s that certain types of polymers. whether chemically or electrochemically driven. The interested reader is referred to the many books and review articles available on the subject [e.17. with particular attention to lithium batteries. The essential structural characteristic needed by polymers to attain this significant conductivity change is a conjugated π-system extending over a large number of monomeric units. 242 . Nafion and related membranes still dominate the fuel cell market. these new protonic gel-type membranes appear to be still under evaluation.g. and to polyanilines. They are called doping processes. The processes that switch conjugated polymers from the insulating to the conducting state are redox reactions. This makes conjugated polymers an interesting class of high capacity electrode materials where the charge injected or released is accompanied by a corresponding ion motion within their structure. as well as on their electronic structure and its evolution upon the doping processes [129-131]. conducting polymers can be switched repeatedly between their doped and undoped states by electrochemical oxidation and reduction processes that may involve a relatively large amount of electronic and ionic charge. The most important feature of conducting polymers is in the reversibility of the doping process. Presently. 126. much effort has been devoted to their use as cathodes in batteries. somewhat similar to the insertion inorganic compounds discussed in Section 7. dopingundoping) process as mixed electronic-ionic conductors. 7. The reader is referred to these references for detailed information. 127]. The limited length of this chapter and its focus on batteries does not allow inclusion of a description of the present status of the polymer electrolyte fuel cells. such as polypyrroles and polythiophenes. The high conductivity of the membranes confirms that their transport mechanism is much less influenced by the humidity level then that of Nafion. p-doping or n-doping. is shown in Figure 7. and to maintain the electrical balance.. a trait common to polyheterocycles. which involves the formation of charged complexes which include polycations or polyanions. in relation to the positive or the negative sign of the injected charge. Thus..1. Thus. conducting polymers may be regarded as ion-insertion electrodes that act during the charge-discharge (i. Many extensive review articles have been published on the synthesis procedure of these conducting polymers. 113. the corresponding structural insertion of adversely charged ions from the redox medium. though intrinsically poor conductors. As for most of the other advanced systems. Consequently. can acquire electronic conductivity approaching that of metals following chemical or electrochemical treatment has triggered intensive research interest in the field. the presently most used proton-conducting membrane.

severe self-discharge [135-137]. More recently. especially of prototypes using PPy or polyaniline as the cathode [132-135]. a PMMA-based electrolyte membrane and a PPy cathode have been successfully assembled and tested [140.e. generally called ‘doping level’ which. such as the previously discussed PEO-LiX blends or the PAN.18. This important concept was first exploited using the PEO-based polymer electrolytes to fabricate thin-film Li/ PPy or Li/PT batteries [138. Considerable effort was paid in the early 1990s to the marketing of lithium-polymer batteries. is proportional to the charge involved and thus to the battery capacity. 243 . a LiClO4-PC electrolyte and a lithium metal anode. The extent of the process is defined by the term y. including a relatively low energy density.. a solution of a lithium salt in an organic solvent. The self-discharge issue has been addressed by considering fully solid-state configurations where the liquid electrolyte was replaced by a polymer electrolyte. such as a reasonably high voltage and a low cost. 139].3. Cells formed by laminating a lithium metal anode.1 Lithium-Doped Conducting Polymer and Lithium-Polymer Batteries Although.or PMMA-based gels.15) The charge process. particularly. gel-type electrolyte membranes described in Section 7. However. In the typical case of a cell based on a PPy cathode. although benefiting from some interesting features. limited power density and. which deposit as lithium metal on the given substrate. The PPy oxidation at the cathode is accompanied at the anodic electrode by the reduction of lithium ions.Polymer Batteries for Electronics 7. in principle.18) which diffuses into the polymer matrix. Significant results have also been obtained using the highly conducting. most battery applications have been confined to the latter. these batteries suffered from some major drawbacks. the electrochemical process can be written as: (PPy)n + nyLiClO4 ⇔ [(PPy)y+ (ClO4-)y ]n + nyLi (7. representing the percentage of moles of the dopant anion over the moles of pyrrole monomer units. involves the p-doping (oxidation) of the polymer with the formation of a polycation whose positive charge is counterbalanced by the ClO4. schematically drawn in Figure 7.electrolyte dopant anion (depicted as A– in Figure 7. In the discharge process the electroactive polymer cathode releases the ClO4. i.2. The initial efforts were mostly concentrated in cells using a liquid electrolyte. attention has been focused on polyheterocycles. The most relevant features of these cells were a very high charge-discharge coulombic efficiency and a long cyclability. Considerable interest was devoted in the early 1980s to the use of polyheterocycles and polyanilines as cathodes in lithium batteries.1. conducting polymers can be used either as anodes (by exploiting their reduction or n-doping process) or as cathodes (by exploiting their oxidation or pdoping process).anions and the Li+ cations are stripped from the metal anode to restore the initial electrolyte concentration. 141].

Other advantages of the dual battery are the low cost. e. 244 .Handbook of Polymers in Electronics Figure 7. 143]. Since both electrodes experience intercalation from different electrolyte species. Laboratory prototypes have been fabricated by preparing the electrodes in the form of thin films backed on metallic substrates and separating them by the polymer electrolyte membrane [142. polypyrrole It is interesting to use the polymer cathodes in lithium-ion cell types. Drawbacks in respect to the standard C/LiMO2 polymer lithium-ion batteries are in the lower capacity and lower operational voltage [144]. this particular cell has been named a ‘dual lithium ion’ battery [142].16) where n is the number of pyrrole units corresponding to one positive doping charge and y is the lithium intercalation level in graphite.anions simultaneously inject into the PPy structure: n6C + (PPy)n + nyLiClO4 ⇔ [(PPy)y+ (ClO4-)y ]n + nLiyC6 (7. By charging the cell. the compatibility with the environment and high power capabilities.18 Schematic representation of the doping process of heterocyclic conducting polymers.g.. Li+ cations enter the graphite structure and ClO4. This concept has been exploited by assembling cells having the structure C/LiClO4-EC-PC-PMMA/PPy. The cell is characterised by good cycling performance and by a total energy density of 300 Wh kg-1.

B. Interface. this will be the type of batteries that will dominate the electronic market in the new millennium. Fabio Ronci and Giuseppe Savo. Elsevier Science. 1995. 2nd Edition. M. USA.M. Parker and P. J. 1994. plastic-like batteries. Wakihara and O. New York. London. 1539. Handbook of Batteries. the final goal being to optimise their response in advanced. D. Scrosati.E. Wenheim. 4 34. Journal of Power Sources. some results of which are reported in this chapter. Dordrecht. UK. Fenton. Linden. Acknowledgements I would like to thank my students and collaborators. B. 1997. D. Lithium Ion Batteries.Polymer Batteries for Electronics The results reported above indicate that a proper choice of the battery components enables the intrinsic potentialities of the polymer electrode and electrolyte materials to be exploited for the development of revolutionary electrochemical devices. 4. Priscilla Reale. London. 11. for their important and dedicated research work. Megahed and B. S. 245 . Electrochemical Supercapacitors: Scientific Fundamentals and Technological Applications. 1998.. Simona D’Andrea.A. Modern Batteries: An Introduction to Electrochemical Power Sources.V. 3. Conway. Undoubtedly. G. Polymer. Ed. Inc. C.E. 6. Vincent and B. 2. Accordingly. Journal of the Electrochemical Society. References 1. Giovanni Battista Appetecchi. Scrosati. Butterworth-Heinemann. McGraw Hill. Conway. 9. Eds. Lithium Batteries. 4. 138. 5. S. Scrosati. The Netherlands. 1995. Luigi Persi. a number of laboratories are currently seeking to enhance the electrochemical properties of conducting polymers by designing suitable materials. 1999. Pistoia. 589. 1998. 8.E. 51. Franco Bonino. 14.79. Fausto Croce. Wiley-VCH. UK. Yamamoto. Megahed and B. 7. 1991. Stefania Panero. 1973. Germany. Paola Romagnoli. Alessandra D’Epifanio. 6.. Kluwer Academic Publishers. 2nd Edition. Wright.

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de Paolis and B. F.M. G. 43. G. K.G. 1996. F.A.B.B. 1996. Gerace. Journal of Power Sources. Appetecchi. Scrosati and S. S. 127. Appetecchi. F. 405. 225. 39. Croce.Slane and M. Edmondson. H. in press.B. 63. L. 369. Scrosati. Electrochemistry Communications. Carroll. 1. 85. G. Pasquariello and K. G. A. 249 . Panero. Oesten. G. 1998. Panero.Salomon. Feuillade and Ph. 16/ 17. Torell and B. G. F. Fontanella. F. S. 7618. G.S. 2. F. B. Scrosati. 1997. Spila and B.G. Chemistry of Materials. Scrosati. 1998. S. Ronci. Scrosati. Scrosati. Greenbaum. C. Ostrovskii. Borjesson. U. Panero. 2399. 173. Stallworth. 66. 64. Scrosati. Wintersgill. G. F. Journal of Electroanalytical Chemistry. Croce. S. Solid State Ionics. F. 9.G. Appetecchi. 1. Ronci. Gerace. Adebahr. 1. Solid State Ionics. F. S.B. Appetecchi. 109. 1-2. 1996. 73. Gerace. Journal of Chemical Physics. S. Dautzenberg. J. L. 19.L.G. 1-2. 1999.Polymer Batteries for Electronics 60. 1994. Scrosati. Electrochimica Acta. Torrell. F. 73. C. 119. Electrochimica Acta.B. Croce.B. Svanberg. Gerace. Scrosati. Gazzetta Chimica Italiana. Croce. E.S. Journal of Physical Chemistry. Brodin. 248. Gazzetta Chimica Italiana. G.M. Croce and B. 68. D. Appetecchi. 126. 1998. 1994. 126. F. Spila and B. Scrosati. 72.B. 77. Appetecchi. E. Croce. 1999. Appetecchi and B. 63.M. 61. F. Torell. Ericson. Romagnoli. D. Dautzenberg. 325. 1-4. M. 74. G. 1997. S. 1975. B. Choe. 71. S. Scrosati. Panero. 5. Passerini and B. 463. Abraham.M.G. Croce. Spila and B. G. H. Abraham. Perche. P. 70. Greenbaum. 1997. Solid State Ionics. 106. 66. Heider and R. 62. E. 69. A. 65. D. 405. Ostrovskii. Croce. Li.E. F. P.M. J. Pasquariello. Gazzetta Chimica Italiana. Appetecchi and B.B. L. B. F.M. Journal of Applied Electrochemistry. 83. L. Choe and D. H.

Journal of Power Sources. G. A. Wang. 10/11. Cherry Hill. Colson. 1997. C. 218. 12. Blyr. S. Scrosati. T. Appetecchi and B. 4161. E. F. Electrochimica Acta. Josefowicz and G. L. 521. B.K. C. Yamamoto. 1983. M. M. USA.S.. L64. R. A. C. Tossici. 77. New Jersey. Tossici. Shokooki. Antonini.. J. 1997.J. Tarascon. Schmutz and J.M. Tarascon. Sconocchia. H. Gozdz. V. Denki Kagacu. R. 1.S.M. USA. 85. assignee.B. Scrosati in Lithium Ion Batteries. Wakihara and O.M. Croce and B. Tarascon. 186. F. Chemistry of Materials. A. Germany. D. 82.318. Nalimova. S. Bellitto and G. G. Journal of the Electrochemical Society. Sigala. 1299. Rosato. Electrochemical and Solid State Letters. 3. 144. Journal of the Electrochemical Society. Journal of the Electrochemical Society. 10.A. 11.159.M. 1992.B. 78. 1996. Bell Communications Research. Scrosati. New York. Chu. Bulletin of the Chemical Society of Japan. J. M. 1-2. Peled in Lithium Batteries. 243. Barrettoni.71. A.C. 6. 84.C. Marassi and B. Amatucci. 1997. Uchida and M. 250 . 66.N. Gozdz. Scrosati. 3. Mc Kinnon.C. Marassi and B. 80. 1991. R. 89. Wiley-VCH.N. 90. Ikuta. F. 1998. 1997. 143. Proceedings of the 37th International Power Sources Symposium. J. R.Handbook of Polymers in Electronics 75. 69. R.R.296. inventors. J. Ogumi and M. 43. Ingo.C. 79. P.S. Academic Press. Greaney. Wenheim. 1105. Appetecchi and B. Farrington. Schmutz. 178. Barrettoni. Scrosati. 1998. 83. 1998. Scrosati. Ed. 76. Tarascon. 1996. 1994. G. Journal of the Electrochemical Society. 1. Marassi.M. 86.C.Y. Larcher and J. Gozdz. Shokoohi. 1996. C. W. Pistoia. Guoha. Gabano. 138. Rosolen. 1998. 1. 88. F. 1443.P. R. G. Journal of the Electrochemical Society. S. 9. Journal of the Electrochemical Society. M. 144. 4. Wakihara. 2859. E. Eds. US Patent 5. R. 81. B. A. Warren. Scrosati. 2776. 139. Z. Amatucci. 143. G. Tossici. 1998.Inaba.

51. T. J. 5317. D. 2. 1998. 98. Miyasaka. David.M. J.O. Y. Journal of the Electrochemical Society. Wiley-VCH.. Ltd. Scrosati.M. 107. 1998. A. 1998. 1999. D.M. Journal of the Electrochemical Society.R. 1992. Panero. 57. Delmas and I. Lee. 145. Retoux. D. Abraham. Schleich. 102. Herterich and D. Kubota. Miyasaka. US Patent 5. Fuiji Photo Film Co. Ed. 96. S. W. Y. Martin and B. 1998. in press. 1997. Journal of Power Sources. 145. 281. Brousse. 1999. U. 251 .O. Besenhard. R.B. 145. Abraham. 595. Solid State Ionics. Electrochemical and Solid State Letters.F. 95. 1996. 1. 44/ 45. 6. 1993. Schleich. Bruce and J. Dahn. 17. Huggins. Pasquerau. 2045. 8. 2615. 1982. inventors. 97. Yang. Peramunage and K. Solid State Ionics. Goodenough. Weinheim. P. MacKinnon and J. Kubota and T. 59. N. Courtney and J. 276. 370. Delmas. 105.G. Handbook of Battery Materials. 144. 100. 1395. Journal of the Electrochemical Society. Solid State Ionics. assignee.R. 1. 99. Idota. Solid State Ionics. Yang and M.O.R. Electrochemical and Solid State Letters. S. Y. 8. Winter and J. M. 1998. 104. Y. Miyaki.A. Savo and B. T. 1. Matsufuji. 113/115.618. I. Maekawa and T.M. Peramunage and K. Besenhard.M. 53/56. Idota. R.R. 1999. Dahn. Germany. Journal of the Electrochemical Society. 90. M.A. 365. Besenhard.I. Scrosati. Defives and D. 785.M Thackeray. M. C. 101. Journal of the American Chemical Society. Winter. Mishima. J. Saadounne. L. 92. C. 2609. C. Journal of Power Sources. Brousse. 87. 68. J. Saadounne and A. Materials Research Bulletin. 1-4.. 94. T. 113/115. 1997. 103. 93. I. Science. 8. 1997. Li. G. Rougier.Polymer Batteries for Electronics 91..640. 1997. 106. W.

1996. Simon Xue.M.H.E. 28-30. 121.C. 118. Ballard. Wieczorek. 97. Chapter 7. 1995. P. Interface. J. F. Lu. B. 1256. Synthetic Metals. D.S. Scrosati. Ohzuku. Retamal and B. Germany. Raducha and K. Ueda and N. Przeworski. 31. G. Journal of the Electrochemical Society. Journal of the Electrochemical Society. Appleby. 12.J. S. www. Yamamoto. D. J. B. C. Granqvist and A. 45. Wieczorek. D. J. 115. 252 .T.27. 1431. 1990. 23. Desbat and J. 5. 8. W. Solid State Ionics. Azens. 113. K.A. 146. 1994. Srinivasan. 1988.co. Chemical Materials. R. Grillone. T. Kouguchi. 116. Kleperis. Weinheim. Macromolecules.Handbook of Polymers in Electronics 108. Kordesch and G. A. Gray. S. D. Ducharme and E.mbi. M.F. J. J. 111. 1997. T. Simader.D. 1121.M. 1996.R. Stevens. G. 124. 610. 120. 142. Wieczorek. 1995. 367. 1995.E. M. 1997. 142. Journal of Power Sources. p. Florjanczyk and W.jp 112. 1991. Wise. 142. M. Cheshire. K. 365. Zygadlo-Monikowska. 1999. 3. 1990. Wang. Zhang. 7.G. 1991. 9. T. 8.D. 1-4.G. 114.S. Manko. 323. L-121. E. Koch.panasonic. Wainright. Solid State Ionics. 123. Vaivars.A. 9. Salvinell and M. 1999. Daniel. Z. Journal of Power Sources. Y. H. A. 347. Wiley-VCH. Jeffrey. Solid State Ionics. 119. R. Mann and J. VCH. 117. Journal of the Electrochemical Society. 1999.R. Enayetullah and J. J. Manna. Germany.125. 122. Journal of the Electrochemical Society. 5. X. Ueda and M. Panero.A. Weng. Osaka. 632. 97. 1-4. A. T. A. Fuel Cells and Their Applications. 4033. Kreuer. Litt. Przyluski and W. 109. 110. 80. Lassegues. 29. Lusis. 1-2.A. Journal of Macromolecular Science A. Weinheim. 119. Solid Polymer Electrolytes: Fundamentals and Technological Applications. Cuellar. Ohzuku.F.

2000. 253 . Prosperi and B. World Scientific Publishing. 34.V. Eds. Osaka. C. H. H. L1. 18. Ando. Mastragostino. Mastragostino and B. Wieczorek. Ono and T. Cambridge. Electrochimica Acta. USA. 1987. Synthetic Metals. P. 142. P. 21. Ed.. Arbizzani and M. T. Panero. 150. 130. 32. 135. 1987.M. 595. Prosperi and B. Ed. 140. 153.R. Chen. Ely and H. Panero. Appelby and F. Appetecchi and B. Arbizzani. Fujimoto. Kohler. 1461.G. Marinangeli. USA. Inganas and R. Momma. Skotheim. Mustedt. Cambridge University Press. H. NY.R. Journal of Power Sources. S. 138. 251. S.Polymer Batteries for Electronics 125. P. Liu and L. Electrochimica Acta. Bittin. Chapman & Hall. Fuel Cell Handbook. Bruce.Q. 1589.A.J. O. Chowdari. UK. New York. 307. New York. G.. 259. 229. 134. 1987. Scrosati. Furukawa and K. Suzuchi. Arbizzani. Ed. 137. NY. J. 36. 131. M. A. G. Giordano. Synthetic Metals. 1993.. Volumes 1 and 2. 1986.. M. 49. Scrosati. John Wiley & Sons Ltd.G. C. Electrochimica Acta. S. Arbizzani. Chemistry and Engineering News. M. 1990. Handbook of Conducting Polymers. Nalwa.B. Nishio. W. Meissner. New York. 1996. H.. D. 35. 127. 28. B. T. Scrosati. C. 1987. 1990. 1989. 132. Nishio in Applications of Electroactive Polymers. Poltarzewski. USA. Bjorklund. NY. 90. 129. London. Kanatzidis. Kakuda. Van Nostrand Reinhold. P. 133. UK. M. River Edge. M. 126. NJ. 1997. N. Journal of the Electrochemical Society. Scrosati in Solid State Electrochemistry. Yoshinaga. Foulkes. Journal of Power Sources. Novak. B. 1991. Scrosati. Scrosati in Handbook of Organic Conductive Molecules and Polymers. Staiti and N. Marcel Dekker. B. Corradini and C. 32. A. Q. Naegele. 136. 1988. Przyluski. Panero and B. Volume 4. S. 128. 17.G. S. K. 1. Scrosati. 1990. T. C663. USA. Journal of Power Sources. 1990. G. A. Mohwald. 13. P. 68. O. Z. R. Mastragostino. in Recent Advances in Fast Ion Conducting Materials and Devices. 139. 1995. Mastragostino. N.

1996. Momma. Scrosati. 1998. 68.B. G. Appetecchi. Panero. 273. 1299. Spila and B. Scrosati. H. T. E. 85. Osaka. E. Panero. 28. A. Journal of the Electrochemical Society. Clemente. E. 144. 2. Journal of Power Sources. S. Spila and B. T. Spila and B. S. Journal of Applied Electrochemistry. Panero. L29. Ito and B. Scrosati. 142. 254 . Solid State Ionics. S. 143. 392.Handbook of Polymers in Electronics 141. 1996. 12. 143. 1997. Scrosati.

various sorts of stimulating energies can change the conformation of molecules. dramatically increases from insulator to conductor upon chemical or electrochemical oxidation [8]. thermal and optical energies. fibres or blocks of conducting polymer expand and contract upon electrochemical oxidation and reduction [1. This results in the deformation of polymer conformation. 10]. and the trans form reverts to the cis form upon illumination by visible light. films.1b). 11-16].1a. Similarly. Kaneto and M. There are many sorts of soft actuators made of polymers [1-3]. as shown in Figure 8. gels [4] and nanotubes [5]. This process is 255 .8 Polymer Microactuators K. shown in Figure 8. This results from the delocalisation of π-electrons and in the change of polymer conformation. is a well-known phenomenon [7]. are different from rotating machines such as electric motors and internal combustion engines. 2. the cis-trans photoisomerisation in azobenzene. The driving force originates from the conformational change of peptide molecules by the chemical energy cycles. At the pristine stage (or in the reduced state).1c and discussed mainly in this chapter. nowadays. The cis form converts to the longer trans form upon illumination by UV light. however. In fact. polyaniline. In the oxidised state. The single bond has more freedom in the rotational and bending modes than that of the double bond. the muscles are constructed in an ordered structure from molecular level to macroscopic level [6]. the mechanism of actuation has being revealed to some extent. changes its bond alternation from the benzenoid form to quinoid form upon oxidation [9. the representative of conducting polymers. In fact. Similarly. such as bending. robotics and replacement of human muscle in the future.1 Introduction Actuators that generate movements and forces. The electrical conductivity in polyacetylene (Figure 8. chemical. Kaneko 8. For example. the bond alternation is reduced and the molecular structure becomes more planar than that of the reduced state. the polyacetylene is flexible because of the single bond in the bond alternation. biomimetic actuators are interesting because of the application to artificial muscles that will be demanded for medical equipment. the details are not known. respectively. expansion and contraction driven by stimulation of electrical. Particularly. In natural muscles.

Handbook of Polymers in Electronics Figure 8.1 Conformational changes of molecular structure. The mechanisms of electrolytic deformation have been classified by three principal mechanisms [17. the behaviour of the electrolytic expansion in conducting polymers. especially polyaniline and poly(o-methoxyaniline) (PMAN) are described. respectively. In mechanism (1). it is desirable to utilise mechanisms (2) and (3). In this section. the insertion is induced by the neutralisation of polymers for oxidation and reduction. To accomplish the larger expansion ratio in the electrolytic deformation of conducting polymers. (2) conformational change of polymer structure due to the delocalisation of π-electrons. upon oxidation and reduction tentatively named ‘electrolytic deformation’ or ‘electrolytic expansion’ in this chapter. the pH of the electrolyte and anisotropy. the dependence of the expansion ratios on oxidation levels. strain. (a) photoisomerisation of azobenzene. The electroexpansion of hydrogels [4] is explained by mechanism (3). the expansion of the polymer is associated with an expanding spring and depends on the morphology of polymer structure. 256 . 18]: (1) the insertion and removal of bulky ions. The magnitude of expansion or contraction depends on the volume of ions and cannot be larger than the total volume of the inserted ions. For mechanism (2). (b) and (c) extension and contraction of polyacetylene and polyaniline. the kind of anions. and (3) electrostatic repulsion between likely charged polycations (polarons and/or bipolarons). with discussion of the basic redox reaction of polyaniline.

21] and a special cell with a pinhole at the bottom [13. For the direct measurement of the displacement. The results obtained using the cell with the pinhole will be discussed. a bimorph actuator [11] has been fabricated. the perpendicular direction [14] and also the thickness direction [20] to investigate the anisotropic behaviour. This method is effective for qualitative measurement and demonstration. The diffusion constant obtained from Equation 8. an Instron testing machine [17. following the methods described in the literature [9. From the simultaneous measurements of the redox current (cyclic voltammogram.% on a glass plate. The films have been examined along the stretch direction. it may be preferable to use soluble polymers. a balance [12].Polymer Microactuators 8. By the application of a stepwise voltage. D is the difussion coefficient and t is the time. the bending is clearly observed. and the ratio of expansion is estimated from the bent curvature of the actuators. Others are hardly soluble in usual organic solvents. Even with an expansion rate at the level of 1%. like pyrrole. CV) and the change of film length (Δl) by the application of linear voltage sweep cycles. the diffusion constant of ions in the film is estimated from the time response of the electrolytic deformation.1 is based on the model that ionic species diffuse from the surface of the film. thiophene and aniline.2. 19]. The diffusion constant is estimated [12] from the initial time dependence of injected charges after the voltage application: f = 4D 1/2 t1/2 π-1/2 d-1 (8. since the expansion is tremendously magnified. d is the thickness of the film. For the measurement of electrolytic deformation. 14] were employed. the relationship between the degree of oxidation and the rate of expansion (Δl/l0. the conducting polymers prepared by the electrochemical methods are obtained as thin films. The cast film obtained by this method can be stretched mechanically to more than 3 times the original length. The emeraldine film can be prepared by casting the NMP solution containing its concentration of 2-10 wt. the change of the film length is picked up by a thread through the pinhole as shown in Figure 8. however.1) where f is the injected charge normalised to the saturated value.2 Sample Preparation and Measurements of Electrolytic Deformation Conducting polymers are prepared by either chemical or electrochemical oxidation of monomers. polymers with substituted long alkyl chains have been found to be soluble in organic solvents. For a measurement of electrolytic deformation. Usually. 257 . In this last method. l0 is the original length) is obtained. Such conducting polymers are. However. such as polyaniline (soluble in N-methyl-2-pyrrolidinone (NMP)). difficult to process. The polyaniline prepared by the chemical oxidation is a powder and the base form is named emeraldine base and is soluble in NMP.1 may also be applicable to the time response of the deformation. Equation 8.

2 Schematic diagrams for the measurement of electrolytic expansion along (a) the film length and (b) the thickness direction.Handbook of Polymers in Electronics (a) (b) Figure 8. respectively. RE and CE are the working electrode. WE. reference electrode and counter electrode. 258 .

LS-ES = 1/2 (Ea + Ec).3. respectively. 259 . respectively. E1/2.3 Electrochemistry and Expansion Behaviour in Polyaniline Film Polyaniline in an aqueous acid solution takes three typical redox stages [9] depending on the degree of oxidation.3 Typical cyclic voltammogram (upper). Figure 8.Polymer Microactuators 8. redox behavior in chemical structures (middle) and expansion and contraction of polyaniline film along the stretched direction (lower). E1/2 is defined as E1/2 = (Ea + Ec)/2. as shown by the cyclic voltammogram curve in Figure 8. where Ea and Ec are anodic and cathodic potentials at the peak currents for oxidation and reduction. The half redox potential. Ea and Ec are the anodic peak and cathode peak.

The level of reduction was determined from the amount of electrically injected electrons in the cyclic voltammogram process of test materials. The polyaniline film contracts 2%-3% by the reduction from the ES state to LS state at around y = –0. Though the radius of benzenesulfonic acid (BSA) is extremely large there is no large contraction since the molecule is too large to penetrate into the film. This extension and contraction behaviour is very similar to the weight change measured by a quartz crystal microbalance [22]. however. the film expands slightly. The LS/ ES reaction is reversible. The LS and the Pas are the most reduced and oxidised states. and the definition is shown as the inset of Figure 8. Then the film contracts slightly. was observed even under light load during the redox cycles [14].3 shows a typical expansion behaviour in a polyaniline film along the stretched direction. y = 0 is the basis of the ES state. respectively. respectively. irreversible expansion. showing that the larger the ion 260 . two electrons are withdrawn and two chloride ions are doped for every four benzene units. and have been found to be insulating.5 and 0. The unstretched film and the stretched film perpendicular to the stretched direction show monotonous expansion during the oxidation LS→ES→Pas and vice versa [14]. 8.4. Here.5. In an oxidation process from the LS to the ES. In the expansion of the film perpendicular to the stretched direction.4. the film starts to expand and shows the maximum expansion at the ES. When the potential was returned from the Pas state. The bottom of Figure 8.4.5 are the LS and Pas states. and then contracts below the potential of E1/2. The result possibly indicates that the dopant ions settle between the polymer chains. By the potential sweep from the LS to higher potentials.2. The result indicates that the electrolytic expansion closely relates to the insertion and exclusion of dopant ions in the film. For the oxidation from the ES to the Pas. The anion radius dependence of the contraction ratio and the diffusion coefficients in polyaniline film at pH = 0 are shown in Figure 8.1. the hydrolysis occurs at the higher oxidised Pas states. The expansion ratio of polyaniline films at pH = 0 strongly depends on the kind of negative ions as seen in Figure 8. for various kinds of electrolytes in polyaniline films at pH = 0 are shown in Figure 8. a creeping effect.4 Dependencies of the Expansion Ratio on the Degree of Oxidation and Dopant Ions The dependence of the expansion ratio [13] on the level of reduction. LS↔ES and returns to the original length. The hysteresis of the curve originates from the non equilibrium condition of the system due to the slow rate of diffusion and also due to thermodynamics.Handbook of Polymers in Electronics The most electrically conductive state is the emeraldine salt (ES) that is between pernigraniline salt (Pas) at the high potential side and the leuco-emeraldine salt (LS) at the low potential side. y. namely. It may be noted that this does not violate the mechanisms (2) and (3) described in Section 8. two electrons are withdrawn and two protons are released. and y = –0.

Figure 8. y. for various kinds of electrolytes in polyaniline films at pH = 0. BSA is benzene sulfonic acid.4 Dependency of the expansion ratio on the level of reduction.Polymer Microactuators Figure 8. and y = 0 is taken as the ES state. The definition of y is shown by the inset.5 Anion radius dependence of the contraction ratio in polyaniline film and poly(o-methoxyaniline) at pH = 0. 261 . l0 is the length of film at y = 0.

the expansion rate scarcely depends on the kind of anion.5 for poly(o-methoxyaniline). results from the conformational change and electrostatic repulsion. However. The dependence of the electrolytic expansion rates in poly(o-methoxyaniline) film on the type of anions is shown in Figures 8. The difference of the magnitude in electrolytic expansion rates at lower and higher pH regions may be attributed to the inserted bulky anions plus protons.6a and 8. Taking this into account.5 pH Dependence of Electrolytic Expansion The observed shift of the redox peaks with change in pH of the solution in an aqueous electrolyte solution indicates that protons are sometimes involved in electrochemical reaction. It should be noted that at pH = 0. The result indicates that at pH = 0 or pH < 1. the E1/2 is independent of the pH. On the other hand. It is important to note that the expansion ratio at the extrapolation to the zero ion radius is a finite value of about 1% and not zero for both films. in the PMAN. whereas at pH = 2 the remarkable dependence is observed.5 in poly(o-methoxyaniline) the electrolytic expansion and contraction are certainly driven by the change of polymer conformation and/or the electrostatic repulsion. suggesting that anions are injected by the oxidation.7b for pH = 0 and pH = 2. Sulfuric acid is considered to be a divalent negative ion. 262 . the electrolytic expansion at pH < 0 (polyaniline) or < 1. where protons are ejected by the oxidation. The gradient of the pH dependence is approximately 60 mV/pH for both curves.Handbook of Polymers in Electronics the more it expands and the smaller the diffusion coefficient. 8.5 (poly(omethoxyaniline). which will be discussed later. at pH greater than 0 for polyaniline and greater than 1.7a and 8.6b. respectively. The finite value results from the conformational change of polymer structure and the electrostatic repulsion. As is evident from these results. E1/2 is pH dependent at pH below 0 for polyaniline and below 1. indicating that the oxidation takes place by the ejection of a proton per one electron [9]. respectively.5 for poly(o-methoxyaniline). the expansion ratio does not show any dependence on the kind of anions at pH = 0. The results proved that the electrolytic expansion is surely due to the doping and dedoping of bulky ions. The pH dependence of the E 1/2 and electrolytic expansion in polyaniline and poly(o-methoxyaniline) [20] are shown in Figures 8.

Polymer Microactuators (a) (b) Figure 8.6 The pH dependency of the E1/2 and electrolytic expansion in (a) polyaniline. and (b) poly(o-methoxyaniline) 263 .

264 .7 The dependency of electrolytic expansions in poly(o-methoxyaniline) films on the kind of anions at (a) pH 0. and (b) pH2. TSA is toluene sulfonic acid.Handbook of Polymers in Electronics (a) (b) Figure 8.

while in the case of polyaniline the oxidation occurs by injection of bulky anions as discussed previously.Polymer Microactuators 8. 23] of an applied step potential.1. current and the expansion and contraction in polyaniline film at pH = 0 are shown in Figure 8. Figure 8. However.8. From the response of the injecting charge normalised to the saturated value based on Equation 8. The typical time responses [13. since the film expansion takes place after the oxidation of film.8 Typical time responses of an applied step potential (upper). The larger the applied potential. the faster is the response of expansion. as the oxidation occurs by ejection of protons in poly(o-methoxyaniline).6 Time Response of the Electrolytic Expansion Usually the diffusion constant in a solution is much larger than in a solid. current (middle) and the expansion and contraction (bottom) in polyaniline film at pH 0 265 . the response of the expansion is slower than the current response. The diffusion constants in polyaniline [13] and poly(o-methoxyaniline) film [23] in various electrolytes at pH = 0 have been summarised. The diffusion constants of poly (o-methoxyaniline) are always larger than that of polyaniline. the diffusion coefficient of dopant ions can be estimated. as the rate of oxidation and reduction are determined by the diffusion of ions in the film.

because of the creeping effect caused by the continuous elongation arising as a consequence of repeated electrochemical oxidation and reduction. The electrolytic expansion perpendicular to the stretched direction is a rough estimation. The electrolytic expansion for the perpendicular direction is larger than that of the unstretched film. anisotropic behaviour of the electrolytic expansion is expected [14. therefore. 266 . 24]. It may be remarked that the evaporation of NMP solution results in shrinkage only in the thickness direction. the cast film has more freedom to expand in the thickness direction than that parallel to the film surface. Therefore. but not in the area. The large expansion ratio for the thickness direction is conjectured to relate to the condensation process of the cast film.Handbook of Polymers in Electronics 8. chains align in the stretched direction.9 [14]. In the stretched polyaniline film. Uniaxial pulling can stretch the polyaniline films by casting from the NMP (used as plasticiser) solution. resulting from the fact that the dopant ions are intercalated between the main chains. The anisotropic expansion of uniaxially stretched film parallel and perpendicular to the stretched direction and of unstretched film is shown in Figure 8.7 Anisotropy of Electrolytic Expansion in Polyaniline Films Polymers are quasi-one-dimensional. and is comparable to that of natural muscles [6]. Figure 8.9 The anisotropic expansion of uniaxially stretched film The electrolytic expansion for the thickness direction in polyaniline cast film [20] shows an extremely large expansion ratio of more than 25% as shown in Figure 8. A similar result was also obtained in the cast film of poly(o-methoxyaniline) for the thickness direction.10.

Actuators fabricated by electrodeposition on gold-coated polyethylene films were studied [11] for the evaluation of expansion ratio and response time. the contraction ratio for the perpendicular direction is slightly larger than that observed in the stretched direction. indicating that the mechanical strength is weaker in the direction perpendicular to polymer chains. 8. 15-17]. Under smaller strains.Polymer Microactuators Figure 8. electrochemically prepared polypyrrole films were used to study the qualitative movement of electrolytic expansion by fabricating a bimorph actuator. a microactuator of several tens of microns made from two layers of gold and 267 . however. Also.8 Contraction Under Strain in Stretched Polyaniline Films The contraction ratio of polyaniline film as a function of strain obtained in the stretched polyaniline film is shown in Figure 8. the contraction ratio decreases more rapidly in the stretched direction than in the perpendicular direction. poly(alkylthiophene) [26] and carbon nanotubes [5]. The movement of bending and stretching of the actuator was demonstrated in electrolyte solution [15].11 [25]. The result indicates that the contraction force is of the order of 1-2 MPa.9 Electrolytic Expansion in Other Conducting Polymers Apart from polyaniline. For example. other conducting polymers that are being studied for electrolytic expansion include polypyrrole [11. which is about 10 times larger than that of natural muscles. At larger strains.10 CV curve (upper) and electrolytic expansion (lower) ratio for the thickness direction in a polyaniline cast film 8.

in which conducting polymer films stuck on adhesive tapes are sandwiched onto a sheet of electrolyte media. microvalves. One of these relates to the oxidation and the reduction of the polymer film process resulting in the bending force doubling. flexible. In carbon nanotube actuators [5]. Two types of bimorph actuators have been proposed [24]. Using polypyrrole films [17]. which consists of two conducting polymer films stuck together on a double-sided adhesive tape.Handbook of Polymers in Electronics Figure 8.11 The typical contraction ratio of polyaniline film against the strain for the stretched direction (//) and the perpendicular direction (⊥) polypyrrole [16] has been demonstrated. 8. The shell-type actuator is self-standing and works in air. and directors of optical fibre [27] are some of the technological applications. One is the backbone type. In these actuators even electrolyte solutions were used. Tweezers. Since dopants transfer from one film to the 268 .10 Applications of Electrolytic Expansion Actuators fabricated by conducting polymers are soft. backbone types [24] were fabricated for demonstration of the bending motion. and lightweight. which can also be replaced by a solid polymer electrolyte. The expansion behaviours of bimorph actuators using poly(alkylthiophene) solids and gels [26] have also been studied. with low voltage drive and strong contraction force. There are some advantages in the use of these bimorph structures. The other is the shell type. the expansion ratio and the force were evaluated by an Instron pulling test machine. the origin of actuation was explained by the mechanism of non faradic charging and discharging on the enormous surface area of the carbon nanotubes.

-S. J. Alexander. 7. 6. A. Y. 1956. Humphrey and A. are other mechanisms operating in a conducting polymer microactuator. Roth and M. Faraday Transactions. 2385. 100. 6. A. E. Science. S. 88. H. A. Hirshberg.W. Y. 2. Wolf. Mazzoldi.G.A. 71.D. 1992. References 1. 1. Huang. Nature. 1991. G. 1992. Kertesz. S. 8. K.G. However. Okuzaki and H. Park and H.H.H. 1988. it should be possible to improve the expansion ratio and the force for practical usage. C.G. 82. Journal of the American Chemical Society. A. Hori. 9. 1978. 1999.W. Wallace. Kaneko. Synthetic Metals.K. A. Macromolecular Symposium. Y. 1992.J.M. Zakhidov. 10. Makromolekulare Chemie. Rossi. 8. By investigating the molecular structure and the higher order structure to optimise the electrolytic expansion. Takenaka. Baughman. The electrolytic actuator can also be used both for positioning and rechargeable battery. Iqubal. Rinzler. B. arising due to the delocalisation of π-electrons and the electrostatic repulsion between the polycations. Gau. Baughman. Journal of Chemical Physics. Journal of the Chemical Society. Drug.M. 6357. 277. K. Ion insertion and exclusion by electrolytic oxidation and reduction are the primary mechanisms. Chiang. M. 269 . Jaschinski. 1340. 1995. Osada. 4. Shacklette.F. R. Barisci. 284. 5.J. Journal of Micromachine Society. R. 2211. S. 1013. Cui. 1986. the electrolyte can be minimised.N. 78. W. it is also evident that the changes in molecular conformations. 3955.G. 4. O. MacDiarmid.C. C. 5. MacDiarmid. Heeger. D. Min and A. MacDiarmid. 242. Gould and R.G. Nikkei Science.A. R. Louis. Y. Baughman. 1-3. 27. Spinks. L. Shirakawa.11 Conclusions The fundamentals of electrolytic expansion in polyaniline films have been discussed. Journal of the American Chemical Society. 2304. Kawami and H.Polymer Microactuators other film through the electrolyte media. J. M. G. Kaneto.D. Oguro.H. Z. Y. 13 (in Japanese). 3.

Kaneko and K. 847. 1735. Inganäs. 1995. Pei and O. Sprinks and G. Oyama. N. 354. 313. 951. Japanese Journal of Applied Physics. 1993. R. US5.. Kawagoe.G. 55-57. 1997. 20. MacDiarmid. 270 .556. Otero. W. 1998. 55-57. M.G. Kajihara. Synthetic Metals. 1. Ed. Murray. 274.H. S. Ura and K. Murray. 1995. Ohmori.I. K. 23. P. inventors. 14. Bechtin in Molecular Electronics. Synthetic Metals. 12.J. 22. 18. X. Kaneto. 26. J.S. 3786. M. G. E81-C. Wallace and R. K. 25. 102. 159. Herod and J.700. Angulo and C. G. Y. 1993. Science. 1009. Kaneto in Gel Handbook. Japan. Santamaria. M. Onoda and M. T. 1-3. Kaneto. Schlenoff. 27. 24. Journal of Electroanalytical Chemisty. K. 34. Smela. 5. Synthetic Metals. Journal of the Physical Society of Japan.T. 1. L837. Elsenbaumer. Kaneto. O. 19. 7A. E81-C. Shacklette. 73. Hayashi. Lundström. 7. R. 15. 1985. E. 3718. The Netherlands.P. 1997. 21.B. 247. Synthetic Metals. T. 7. Japanese Journal of Applied Physics. Kaneto. Yoshino.M. University of Pennsylvania. K. 1995. Synthetic Metals.L. Kaneto. K..H. Baughman.. Lazarev. 1999. 17. 1995. S. 1146. 3713. 3. M. Chemisty of Materials. N. 34. 1996. P.R. 13. Inganäs. Takashima. 16. T. Osada and K. Kaneko and K. 1350. 1993. Kaneko and K. Daifuku. assignee. 1991. Eds. Takashima. E.F. IEICE Transactions.M. E. IEICE Transactions. G. Iwamoto. L. Y. Y.G. Min and A. 7. Wallace. K. Rodriguez. 54. 74. M. Chen and O. P. 1995. Spinks. T. 84. Fukui. M. 268. Kudo.W.Handbook of Polymers in Electronics 11. Kaneto. Kluwer Academic Publishers. 1989. Yamamoto. Kaneto. Q. H. Ohsaka and N. 1064. M. 1998. Gandhi. Inganäs and I. Kaneko and W. 7B. Plichta and C. 267. Synthetic Metals. Burford.

and general articles have been published about organic thin films. With this base of knowledge. Hiratsuka 9. Many newer surface science techniques. spectroscopic. Organised films are now being designed to perform new and special functions. However. and dynamic behaviour for best optimising a film for a specific research study or specific application. A number of books. many new compounds and polymers have been synthesised and made into thin films by a variety of techniques. Clearly. polymeric films fabricated by either oxidative deposition or polymerised in situ are rapidly becoming more popular. Fundamental studies are also in progress for the characterisation of the optical. it is hoped that this leads to our understanding of intermolecular interactions. 271 . cooperative effects can change the behaviour of any film. Significantly.1 Introduction In materials science. could influence behaviour. organic films were considered to be too fragile with insufficient purity to give reliable and consistent properties to make thin films for practical use. including energy transfer between molecules in the film and between layers. address specific details about the structure and morphology of these organic films. Other related topics include polymer surfaces and interfaces [5]. knowledge of the morphology of the substrate is needed.9 Membranes for Electronics I. Although the preparation and study of LB films are still very active areas of research. 4] and imprinted polymers. this trend is changing with the discovery of new materials. The extent of interaction. thin films are designed to have a desired molecular order. These organic films are carefully constructed to avoid the common problems. The films should also have several different material properties in a restricted geometry. Recently. and electrical properties. Many intensive scientific investigations are focused on the preparation and characterisation of new polymeric organic films. reviews. conducting films [3. In the past. self-assembled films [1. Karube and A. Extensive scientific studies have generated a wide variety of useful knowledge for the development of new thin film materials that exhibit specifically desired behaviour. designed and developed for semiconductors and dielectric materials. both laterally and vertically between the layers and substrates. 2]. energy transfer. such as Langmuir-Blodgett (LB) films.

This leads to wetting phenomena. One can find applications in such diverse fields as tissue engineering. In this regard. polyacrylamide. e. The reagent matrix must be carefully selected to mitigate or eliminate non uniformity in a reagent’s concentration due to improper mixing. The coated matrix must have the desired pore size and pore distribution to allow penetration of the analyte being measured as well as having the desired gloss.. the polymer should have good adhesion to the support substrate and should show little or no change during handling or manufacture of films. surface pre. One example of the application of polymers in coatings is use as a binder. These materials interface between two layers of different materials. Polymeric binders used in multilayered coatings include various emulsion polymers. Polymer surface-based chemistries for biosensors are gaining importance and will continue to see growth in demand in the near future. gelatine. viscosity.Handbook of Polymers in Electronics Another field of scientific research is ‘interface materials’. 272 . Polymers are thus finding ever-increasing use as diagnostic medical reagents [6]. It also affects molecular motion. superior mechanical properties and potential for adsorbing enzymes properties in a restricted geometry. copolymers of vinylpyrrolidone and acrylamine. melting and other processes. solid content. solubility. and hydrophilic cellulose derivatives such as hydroxyethylcellulose and methyl cellulose. Polymers must be carefully screened and selected to avoid interference with the chemistry. Today’s diagnostic medicine is placing demands on technology for new materials and specific applications. film forming temperature and particle size should be carefully considered. gas or ionic diffusion through the film. Therefore. agarose. residual initiators. Biosensors have been widely researched and developed as a tool for medical and environmental monitoring. Polymeric materials for the purpose of biomedical applications are presently of growing concern. surfactants. and lubrication. polyvinylpyrrolidone. They are designed to produce a digital electronic signal that is proportional to the concentration of a specific chemical or a set of chemicals. The properties of polymers. The nature of the interfacial organic thin films contributes to the orientation of the molecules and their packing. which is necessary to integrate the system chemistry.and post-treatment creating specific interactions are active areas of research. sensitivity and versatility of biosensors and in medical diagnostics to measure vital analytes. Polymers can be prepared with several compositions and modifications while their physical properties including morphology can be regulated by variation in their composition and modifications. This is often studied between two different polymeric layers. polyvinyl alcohol. setting or non uniform coating thickness. implants. phase transitions. swelling of the polymer binder due to the absorption of the liquid sample may or may not be advantageous. adhesion.g. Polymers are used to enhance the speed. In general. including lateral diffusion. swelling characteristics and surface energetics. Depending on the system. therapeutic devices and diagnostic assays. Emulsion polymers have a distinct advantage over soluble polymers due to their high molecular weight. adsorption. aqueous-based emulsion polymers and watersoluble polymers are being extensively used.

reproducibility and reusability. field-effect transistors (ISFET) and surface plasmon resonance (SPR) techniques have also been utilised. The first organic photoconductors were charge transfer polymers that can generate and transport charges. Without these resists.Membranes for Electronics The biological recognition element is generally chosen from the enzymes. In the case of magnetic disks. lubricants were added 273 . There has been an increasing utilisation of organic thin films in many new electronic. To overcome these problems. are also used as insulating layers or for packaging. Layer by layer. High temperature polymers. In later versions. quartz crystal microbalances or semiconducting devices. receptors. polyimides did not cause problems. photon counters. Further treatment includes diffusion of various semiconductor elements and metallisation for conduction lines. such as polyimide and other related polymers. storage density is demanded. This process is employed either in wet or in dry conditions. Not only have the liquid crystals been improved. The transducers could be electrodes. Polymers as liquid crystal displays are now ubiquitous in watches and flat panel displays. The performance of the biosensors is governed by the techniques used in combining these two components. Further. sensitivity. the total package is developed. thermisters. Subsequently. This is known as the photolithographic process. these functions were separated into different polymer layers. An essential technique in developing biosensors includes immobilisation of the biological components to the surface of the transducers. unpolymerised sections are removed. tissues and microorganisms due to their excellent selectivity for target substances. This process required a large sputtering chamber and the films obtained were not uniform resulting in the development of cracks. Organic photoconductors are used in copiers and printers. Ion-selective. The recent trend in biosensors is towards miniaturisation with semiconductor microfabrication or micromachining techniques [7-9]. antibodies. This has led to the surface modification of organic materials for specific applications. However. These polymers are spun onto the semiconductor and exposed to the circuit pattern leading to main chain scission or crosslinking. optical and mechanical devices. Current research is now directed toward finer features in the patterns and changes in the surface characteristics for subsequent layers. Photoresists and electron-beam resists are the key to the success of VLSI electronic circuits. but also the surface treatment and manufacture processes have been significantly advanced. The immobilisation matrix (interfacial design) should feature a thin film in order to maintain the desired sensor characteristics such as response time. Both of these problems now seem to be under control. The adhesion of metal layers to polyimide was at times not so good. each of which could be handled easily. most electronic equipment would not exist. sputtered or thermally oxidised SiO2 layers were used. Efforts to reduce the bit size by manoeuvring the read-write head closer to the disk surface tends to generate new problems such as stick or friction. which is part of the semiconductor fabrication technology.

Polypyrrole. For example. polyaniline and polythiophene have all been used. Direct electron transfer between GOD and the electrode can also occur. implantation of medical devices and artificial organs. In the first approach. They have made a large number of such polymers and evaluated their electrochemical characteristics [14]. In the third approach. A number of groups are studying friction. The polymer penetrates and binds the enzyme to the electrode. lubrication. In 1967. much work has been done on the exploration and development of redox polymers that can rapidly and efficiently shuttle electrons. The mediator could also be a redox polymer. As for GOD. enzymes are used. the polymers are functionalised not only as immobilised matrices but also as electron mediators. and adhesion from a fundamental point of view [10-12]. Glucose was oxidised to glucono-lactone by the enzyme of glucose oxidase (GOD). the enzyme is reduced (or oxidised) by Dglucose (substrate) and then this reduced (oxidised) enzyme is oxidised (reduced) by an acceptor. in the case of GOD. In this approach. Thus response time and sensitivity are improved. An enzyme-immobilised electrode is not essential in this system but an oxygen electrode is required for measuring changes in the dissolved oxygen concentration. prostheses and many other medical fields.Handbook of Polymers in Electronics to the disk surfaces. Their most stable reproducible redox polymer was poly(4-vinyl pyridine) to which Os(bpy)3Cl2 274 . usually on top of an amorphous carbon coating. Sanyo introduced electrolytic capacitors in 1983 based on tetracyanoquinodimethane (TCNQ). Since that times several other capacitors have been introduced into the marketplace. The second approach uses an enzyme-immobilised electrode and the commonly used immobilising matrices are polymers. The enzyme is immobilised close to the electrode. Polymers have found applications in such diverse biomedical fields as tissue engineering. This application of polymeric gel materials is growing very fast. These capacitors range in values from 0. Various approaches are used for diagnostic applications of these biomaterials. This system is polarised at a suitable redox potential. and so only a small amount of reaction product is needed. Updike and co-workers investigated a promising approach to glucose monitoring in the form of an enzyme electrode [13]. allowing the read-write head to be much closer to the magnetic storage disk surface. Several research groups have wired the enzyme to the electrode with a long chain polymer having a dense array of electron relays.1 μF to 200 μF and have low equivalent series resistance and high frequency impedance with good reliability and lifetimes. Gregg and Heller have done extensive work on osmium-containing polymers. the nature of the enzyme reaction is exploited. the enzyme was incorporated and immobilised in the polymer gel matrices. oxygen consumption is measured. In the past decade. The most popular have been fluorinated polymeric ethers.

To make it water soluble and biologically compatible. and GOD to produce a crosslinked biosensor coating film. FADH2 (in close proximity to the GOD active site). biosensors based on these redox polymers give good response and stability. Surridge and co-workers have carried out electron-transport rate studies on an enzyme electrode for glucose using interdigited array electrodes [16]. No mediation occurred when ferrocene was attached to a non silicone backbone. functionalisation of conductive polymer films is essential. an electron relay that transfers redox equivalents (electrons) from the active site of GOD’s cofactor to the electrode surface is needed. The resultant redox polymer was water insoluble. enabling a patient to take corrective measures. the enzyme electrode should be fabricated in a mass fabrication oriented technique and should be capable of being miniaturised.or hypoglycaemia. For integrating biosensors with electronics. The resultant enzyme/albumin layer was crosslinked by butraldehyde. Boguslavsky and co-workers used a flexible polymer chain to put electron relays [15]. Their polymers provide communication between redox centres in glucose oxidase (GOD) and the electrode.g. polyaniline and polythiophene are formed at the anode by electrochemical polymerisation [17]. For integration of bioselective compounds and/or redox polymers into conductive polymers. In order to transfer electrons directly between the electrodes and enzymes. The choice for an artificial electron relay depends on a molecule’s ability to reach the reduced flavin adenine dinucleotide. undergo fast electron transfer. They developed an electrodeposition technique to electrically attract GOD and albumin onto the surface of the working electrode. and then transport electrons to the electrodes as rapidly as possible. Therefore. polyethylene glycol diglycidyl ether.2´-bipyridyl) osmium chloride) had been attached to the pendant pyridine group. They also developed a biocompatible polyethylene glycol/polyurethane copolymer to serve as the outer membrane of the sensor to provide differential permeability of oxygen relative to glucose to avoid the oxygen deficit encountered in physiological tissues. This polymer is water soluble and the newly introduced amine groups can react with a water-soluble epoxy. incorporating such a biosensor into a closed-loop system with a microprocessor and an insulin infusion pump could provide automatic regulation of the patient’s blood glucose. Johnson and co-workers used two novel technologies in the fabrication of a miniature sensor for implantation in the subcutaneous tissues of humans with diabetes [18]. In contrast. Conductive polymers such as polypyrrole. Furthermore. e. A biosensor providing continuous readings of blood glucose would be most useful at the onset of hyper. 275 . Such coating films produce high current densities and a linear response to glucose up to 600 mg/dL.Membranes for Electronics (tris-(2. Integration of enzymes and mediators simultaneously should improve the electron transfer pathway from the active site of the enzyme to the electrode. There is a pressing need for an implantable glucose sensor for optimal control of blood glucose concentration in diabetics. Their ferrocene-modified siloxane polymers are stable and non diffusing.. Heller and co-workers partially quaternised the remaining pyridine pendants with 2-bromoethylamine.

such as plasma polymerisation.g. These new technologies will certainly have an impact on rapid chemical analysis by the turn of this century. dry processing is more advantageous. VLSI and related 276 .Handbook of Polymers in Electronics Recently. This is possible as detection instruments can be designed compactly. pinhole-free. non linear optical (NLO) and molecular devices [22]. A plasma-polymerised film offers a new alternative [19]. and stable. it is of interest to develop polymer thin films of high quality for a variety of industrial applications. flat-surface structures and are chemically and mechanically stable. very thin. The first includes wet processes like LB. e. mass reproducible and thin polymers. spreading. The plasma-polymerised film is achieved in a glow discharge or plasma in the vapour phase. which can produce accurate. Applications also include chemical. are frequently used to make polymer thin films [24-26]. surgical and critical care units as well as in homes. The other is dry processing. even for electronic and optic-based applications. organic thin films have received a great deal of interest due to their extensive applications in the fields of mechanics. Exactach (Medisense). microelectronic devices. In general. physical and biological sensors. there is a market for small. In spite of a large number of studies in this area. the characterisation techniques. The polymers fabricated by conventional methods may have potential problems such as the difficulty of preparing thin (<1 μm) and homogeneous films. In the following sections. This is mainly because organic films often show poor thermal and chemical stability and poor mechanical toughness [23]. dipping or solvent casting methods. electronics and optics [20. the CVD methods. A typically important example is that of blood glucose determination on very small blood volumes (<5 μL) obtained by a finger pricker. only a few of these materials have been successfully used. and silicon-base arrayed systems (I-Stat) have appeared in the market. Fabrication of polymers for these small and integrated sensors should be by the new processing technologies. disposable electrochemical tests in the emergency room. Comparing these two technologies. Such films are thin (< 1 μm). commercial electrochemical microbiosensors. 21].2 Plasma Polymerisation The polymers employed for integration between biomaterials and electronics should be mass-producible. such as physical vapour deposition (PVD) and chemical vapour deposition (CVD). Of these methods. Certainly.. Ultrathin polymer films can be prepared using two kinds of technology. 9. Therefore. mainly because its technology originated from semiconductor or VLSI processes. properties and applications for both electronical and biological aspects of plasma-polymerised films are described.

electrons and other species which are energetic enough to break any bond.2. plasma polymerisation has been utilised for the processing of pinhole-free and sub-micron films [34]. Hence. For the time being.. Hence. applications to electronic fields have been carried out and several practical examples for surface coatings and corrosion protections can be found. most of these materials were not intended to control the character or the structures of the reaction products.e. but the number of reports related to this field is currently on the increase. Plasmapolymerised films for chemical and biochemical applications are still rare. 9. extensive work has been done on characteristic studies and improvement of instrumental and processing technologies. a free-radical reaction could be a dominant process for plasma depositions [36. The plasma-state polymerisation depends on the presence of ions. there have only been a few examples of plasma polymerisation compared with other ordinary polymer processing techniques such as chemical or electrochemical synthesis. In spite of the difficulty. In 1931. The initial study on the nature of well-defined adhesion and uniformity structures for metal coating films was reported by Goodman [33]. Thenard [29] and Wilde [30] reported that solid materials were produced on the reaction wall after discharging in hydrocarbon vapours.1 History Organic chemical reactions induced by discharge have been used and studied since the 1800s [27. plasma polymerisation is a process of preparing thin polymer films. In 1874. Among the several possible mechanisms which have been expressed. Among all the VLSI technologies. 28]. plasma-induced polymerisation and plasma-state polymerisation are presumed. 9. i. This is partly because of the difficulty of controlling the polymeric reactions. 37]. The resulting decomposition products of the plasma recombine by a free- 277 . two types of reaction. Stewart [32] produced insulating film from hydrocarbon gas under a high-pressure condition of 10-5 Torr.2 General Characteristics Plasma polymers are deposited as a thin film and/or as a powder on surfaces contacting a glow discharge of organic or organometallic feed gases.Membranes for Electronics technologies are very compatible with mass-production miniaturisation and integration processes.2. which involves reactions between plasma species. The plasma-induced polymerisation is the conventional free-radical induced polymerisation of molecules containing unsaturated carbon-carbon bonds. Plasma polymerisation is a specific type of plasma chemistry. between plasma on the surface [35]. Following this work. Brewer and coworkers [31] reported that insoluble yellow coloured materials were produced when applying the glow discharge to methane at room temperature. However.

2. Films are often highly coherent and adherent to a variety of substrates. The plasma polymerisation reactions are especially influenced by the monomer gases and the power supplied. So these films have been used in a variety of applications such as permeability selective membranes. 9. Plasma-polymerised films are in general chemically inert. glasses. protective coatings. Ultrathin. plasma polymers do not consist of chains with a regular repeat unit. optical and biomedical films. Plasma-polymerised films can be easily produced with thickness of 10 nm to 1 μm. Feed gas composition. Unlike conventional organic polymers.Handbook of Polymers in Electronics radical termination reaction. Polymerisation may be employed without the use of solvents. it is possible to fabricate a chemically functionalised surface with a desired thickness. and thermally stable.3 Synthesis of Plasma Polymers The physical and chemical properties and the deposition rate for plasma-polymerised films depend on the following factors: • • • • • • Reactor type. 278 . pinhole-free films may be prepared. The chemical structure and physical properties may be quite different from the conventional polymer derived from the same starting materials. and electrical. mechanically tough. such as saturated alkanes or benzene [38]. but tend to form an irregular three-dimensional crosslinked network. Plasma temperature. With careful control of the polymerisation parameters. The most notable aspect of plasma polymerisation is that the thin polymer film can be prepared from almost any kind of organic vapour. This allows the polymerisation of unconventional starting materials. Several review articles have already discussed the effect of such properties. Flow rate of feed gases. including conventional polymers. and metals. Frequency and power of the excitation signal. and Substrate position. There are several advantages of plasma-polymerised films over conventional polymers: • • • • • • The starting feed gases used do not have to contain the type of functional groups normally associated with conventional polymerisation. insoluble.

1): Internal electrode reactor with dc power supply Internal electrode reactor with RF power supply External electrode reactor with RF power supply Electrodeless microwave (2.3.1 Reactors for plasma polymerisation 279 .2. The most widely used reactor configurations for plasma polymerisation can be divided into the following types (see Figure 9.45 GHz) reactor Figure 9.1 Reactors Many authors [39-42] have provided detailed studies of experimental configurations.Membranes for Electronics 9.

The working conditions and apparatus geometry can significantly influence the extent of ion bombardment on the substrate. Each differs in power supply. However. and sample position. However. Usually inductively coupled tubular reactors cannot be uniformly coupled to the power supply while operating at low pressure (<< 1 Torr). ceramics or alumina as reactor materials. Many experimental arrangements have been reported. An applied electrode potential oscillates around a cathode selfbias potential. On the other hand. flat bed. diode. The tube geometry is variable [4446] and the position of the sample stage may vary from upstream to downstream of the monomer gas flow in order to obtain different polymer composition and properties.. Metal plate electrodes are aligned parallel with the reactor. contaminating the target. 280 . etc. this system is rarely used to develop the plasma polymerisation because it breaks the insulation between the electrodes due to polymerisation on the cathode by the dc glow discharge. • Internal electrode reactors with radio frequency (RF) power supply The RF power supply is coupled to the system by means of a blocking capacitor (capacitive coupling). quartz. The vacuum chambers can either be made of glass or conductive materials. metallic reactor material can be sputtered. but the design and arrangement of the cathode requires special attention.Handbook of Polymers in Electronics • Internal electrode reactors with direct current (dc) power supply Internal electrode reactors have several names. • External electrode reactors with RF power supply External electrode reactors can be used either capacitively or inductively coupled. The polymer is generally collected outside the glow region [48]. In the case of bell jar reactors. the metallic shield reactor surrounding the electrode improves the glow confinement inside the inter-electrode space. • Electrode-less microwave or high frequency reactors The name of these reactors implies that no impurities can be sputtered off and incorporated into the growing films. such as metals. parallel plate. e. However. reactor geometry.g.56 MHz. planar. which is prone to being negative. Insulating tubular reactors may be made of glass. The working frequency of the most commonly used power supplies is 13. coupling uniformity increases with increasing working pressure [47]. A microwave (MW)-powered system is characterised by tubular quartz or Pyrex reactors and by a resonant cavity coupled with a power supply typically in the resonant cavity. Power is transmitted from the power supply to the monomer material by a capacitor and a coil. no particular care is essential about the grounded electrode. Either an alternating current (ac) (1-50 kHz) or RF field is used. the electron energy distribution and the production of active species [43].

where E is the electric field activating the plasma and pg is the pressure in the plasma. The deposition rate is limited by the supply of the feed gas. λ.2. The paper said that the large differences between the two systems could be the production of different active species and the different roles of ions and electrons. D’Agostino and co-workers showed that unsaturation of the feed gases always causes an increase of the maximum deposition rate by one order of magnitude and a shift to higher flow rate [50. The effects of the pressure on the plasma polymerisation process include: • • The effect on residence time: the residence time is directly proportional to the pressure.1) where r is the radius of the molecule and N is the gas density [53]. The effect on mean free path: the mean free path of a molecule. The effect of the position of the monomer inlet in a capacitively coupled belljar reactor has been studied [41. The polymer powders are formed between 200 mTorr to 2 Torr under relatively low flow rate conditions. The flow rate is controlled by either a mass flow or a needle valve. The effect on average electron energy: for RF plasma the average electron energy is proportional to E/pg.3. The pressure can affect the mean pathway by affecting the gas density. 9. which connects between a gas reservoir and the reaction chamber. The exclusion of powder formation will occur at above 2 Torr in which low mean free path. in a gas is expressed as: • λ = (π r2 N) / 4 (9. the position of the inlet was found to affect the efficacy of the resultant plasma polymer as a reverse osmosis membrane. At a high flow rate.Membranes for Electronics The differences between the MW discharge and the RF discharge have been discussed [49]. 51]. The effect of the direction of flow on deposition rate distribution has received some attention.2 Gas Parameters The main parameters of the gas are flow rate and pressure. long residence time and relatively high electron energy are required. the deposition rate decreases and the activated species may be prevented from reaching the substrate. The chemical affects associated with low power plasma are observed at high pressures. 52]. In the latter work. 281 .

Therefore. Thus most plasma polymerisation is carried out at pressures below 1 Torr. the deposition rate of the film increases with power at first and then becomes independent at higher values of power [43]. These factors are essential for the characterisation of plasma polymers. combined pyrolysis/gas chromatography/mass spectroscopy (P/GC/MS). 55]. Auger electron spectroscopy (AES). an increase of power is obtained by both an increase in potential drop between electrodes and an increase in current density on the electrodes.3 Power Parameter Increase of power will result in an increased density of energetic electrons and more frequent ion bombardment on the electrode. The relationship between the deposition condition and the resulting structure of the compositions has been investigated and reviewed [56. Plasma polymers may have a high degree of crosslinking and may contain unsaturated bonds. the quantities of solid plasma films are very small.3 Characterisation of Plasma Polymers Plasma polymer films are generally considered to be amorphous. 57]. typically milligrams. In most plasma polymerisation experiments. inhomogenity in deposition rate is caused by an increase in pressure. sophisticated tools should be used instead of the analytical methods generally used for conventional polymers.2. At constant pressure and flow rate. which results in an increase in the energetic electrons. The structures of plasma polymer films have been studied by numerous modern analytical techniques. the power has been reported to increase with an increase in current.3.Handbook of Polymers in Electronics However. atomic absorption 282 . Both effects result in an increased density of energetic electrons and increase bombardment of the electrode by energetic ions. For an RF discharge. The chemical composition and the nature of the internal bonding of plasma polymers are usually different from conventional polymers synthesised from the same monomer units. X-ray photoelectron spectroscopy (XPS) or electron spectroscopy for chemical analysis (ESCA). UV absorption spectroscopy. secondary ion mass spectroscopy. These include IR and Fourier Transform IR (FTIR) spectroscopy. and the polymers are generally insoluble in organic solvents due to their high degree of crosslinking. 9. ion scattering spectroscopy. chromatography. electroluminescent spectroscopy. For a dc or ac glow discharge. in order to obtain the increased interaction of the plasma with a polymer surface to obtain homogeneous films [54. 9. solid state NMR spectroscopy.

neutron activation analysis. and for wettability were explained. metal/polymer interfaces in structural adhesive joints. it has been used to quantitatively measure the concentrations of functional groups and the crosslinking density of plasma polymer films [42-44]. 9. differential scanning calorimetry (DSC). Thus. electron spin resonance (ESR) spectroscopy. fluorinated plasma polymers are most widely studied by XPS [38]. The penetration depth of the X-ray is about 5 nm and this yields the relative population of elements at the surface. Although primarily a qualitative analytical tool. elemental analysis. Most of these investigations are on the interface between polymers and inorganic materials. 9. for instance. scanning electron microscopy (SEM) and atomic force microscopy (AFM). Consequently. 283 .3. reflection high energy electron diffraction. Since plasma polymers are deposited as extremely thin films. 9. and cation diffusion along polymer/metal interfaces under an applied electric potential. Among these analytical tools. X-ray diffraction. This method is most effective when the nearest neighbour atom is highly electron withdrawing. XPS is ideally suited for the determination of the chemical properties of these films. IR spectra might be obtained by depositing the plasma polymer on IR transparent substances or on other surfaces by using attenuated total reflectance (ATR).4 Applications of Plasma Polymers Both electronic and medical applications of plasma polymers have been reported [5461]. wherein protective films for microcircuitry. transmission electron microscopy (TEM). In another reference.2 XPS XPS (or ESCA) is a powerful tool for analysing the surface of plasma polymer films.3. nuclear elastic recoil detection. XPS can also be used to obtain information regarding variations in depth by means of angle-resolved spectra and ion milling. IR and FTIR spectroscopy and XPS are frequently used to investigate the chemical and physical structures of films [54]. XPS is a technique in which the number and energy of core level electrons expelled from atoms are analysed on their absorption of X-rays.1 IR Spectroscopy IR spectroscopy can be used for the identification of functional groups in plasma polymer films. XPS is also suitable for functional group identification. thermogravimetric analysis (TGA). more specific aspects for electrical and electronic applications [59] were treated.Membranes for Electronics spectroscopy. The electron energy observed for a given atom will also be influenced by the electron withdrawing power of the nearest neighbour atom. The use of such film for surface treatment has also been examined.

4. dimensions or geometry of the substrates. high thermal resistivity. Another packaging material is plasma-polymerised hexamethyldisilazane. and hermetic encapsulation into a series of in-situ vacuum processes.2 Insulator Thin films of high thermal resistivity and electrical insulation were prepared by plasma polymerisation of silazane and subsequent pyrolysis in air. The hybrid films for the pinhole-free electrical insulators were prepared using hexamethyldisiloxane (HMDSO) and silicon monoxide (SiO) [64].1 Packaging Due to their excellent electrical and thermal properties. The author described how the chemical constitution of the films transformed into a silicon oxide type and a polycrystalline structure after the pyrolysis process [63]. and very good insulating properties in a broad range of temperatures. Most of the conventional polysiloxanes are either gel-like or rubbery materials. The HMDSO hybrid films were prepared on the substrates by evaporating SiO during HMDSO plasma polymerisation in RF discharge. The films for insulators can be fabricated not only by inorganic compounds as mentioned above. surface treatment. polysiloxanes are some of the most prevailing materials used in electronic encapsulation applications. These thin films are useful for conformal coatings in hermetic packages and as dielectrics for integrated circuits or multichip modules.Handbook of Polymers in Electronics 9. but also by organic compounds. which has a character of moisture impermeability and which could be used for protection of thin film nichrome resistors [61]. plasma-polymerised films have good mechanical strength and resist cracking up to 25 microns thickness. 9. The plasma-polymerised films combine the features of surface cleaning. SiO was evaporated by heating in RF plasma consisting of HMDSO and oxygen at a pressure of 10-4 Torr. Plasma-polymerised films with uniform thin 284 . Plasma polymerisation/vapour deposition (PP/VD) was applied to provide functional hermetic encapsulation of integrated circuits [62].4. Complementary metal oxide semiconductor (CMOS) circuits fabricated by a plasma process immersed in Ringer’s solution were tested for a year. However. The film had strong adhesion. functional hermetic encapsulating polymer films with a total thickness of 5 μm have been produced. independent of the composition. and have limited applications in areas demanding high mechanical strength of the coating material in addition to passivation properties. The result showed unchanging device performance parameters characteristic of hermetically encapsulated integrated circuits. Elastic thin films have been developed using some proprietary silicon-containing compounds [60].

This polymer was discovered to have two states of electrical conduction. The reactor incorporates an electrode-less or inductively coupled power source and a thermally activated sublimation and pyrolysis chamber for vapour deposition of Parylene C.4. A structural and electrical survey for conductive phenomena was performed using acetonitrile plasma polymerised film [68]. 285 .4. This design allows for the in-situ application of a thin adherent coating of plasma-polymerised methane followed by a thicker coating of Parylene C as well as serving as a ‘bio’ interface. The deposition of polythiophene lowered the barrier height. Electrical conductivity of the iodinedoped material decreased by five orders of magnitude and the iodine doping caused a serious structural change. Plasma-polymerised thiophene for passivating the surface defects on GaAs has been employed [70]. Parylene C (poly(chloro-p-xylene) was used as an electrical insulator for the polymerisation [66]. The synthesised films had good resistance to heat and chemicals. reduced the surface recombination velocity and increased diffusion length.9. The paper showed the passivation of GaAs surface was made possible by sulfur present in an overlayer. A novel reactor was designed to deposit thin adhering and insulating films to common semiconductor materials. quartz and glass. SEM and X-ray diffraction. XPS. Tetramethyltin (TMT) and diethylzinc (DEZ) were deposited on several substrates such as polypropylene. 9. SnO2. Electrical conduction in the high conduction state was sensitive to the nature of electrode material. Electrical conduction in the low conduction state was unaffected by the electrode material.10perylenetetracarboxylic dianhydride (PTCDA) [67]. provided by the thin film of plasma-polymerised thiophene. These plasma polymers have been considered as passivation or insulation layers of ICs and other electronic devices. Organometallic compounds were used to fabricate semiconductive thin films on different substrates by glow discharge polymerisation [69]. Adhesion between the plasma polymer of methane and Parylene C could be improved by incorporating an intermediate layer of plasma polymerised para-xylyene film.Membranes for Electronics organic layers [65] can be prepared from almost any organic compounds. It has been reported that a plasma polymer copolymerised from allylamine and ethylene could be used as an orientation layer for a liquid crystal [69]. The physicochemical properties of the deposited films were characterised by FTIR.3 Semiconductive Films A doped material was prepared by plasma polymerisation using 3.

Dry resist coating is a key technology to replace a conventional wet lithography.56 MHz and a pressure range of 0.4.5 Resist Films Lithography is indispensable for the fabrication of integrated circuits. The films were very smooth and pinhole-free.4.4 Conductive Films A conducting plasma polymer was processed using TCNQ with quinoline [71]. However. The results showed that the plasma-polymerised quinoline and TCNQ had conductivities of 10-12 Ω-1 cm-1 and 10-9 Ω-1 cm-1. There have been several papers and reports about plasma-polymerised resists [76-78]. The deposition conditions included a discharge frequency of 13.Handbook of Polymers in Electronics 9.6 Ultrathin Polymer Films It is well known that thin polymer films with thickness about 100–1000 nm can be prepared by plasma polymerisation or electron beam and UV irradiation of organic vapour.8 Torr. respectively. Ultrathin hydrocarbon films (C2H2 as feed gas) were deposited on electronic grade n-type silicon wafers. influenced by the shortrange molecular order. 286 . using metal-containing monomers blended in the resist polymer as resist sensitiser. or a hydrocarbon/argon mixture. 9.5-0.4. Copolymerised resists for high sensitivity have been produced [76-78]. while the charge transport influenced by the long-range order did not occur in these systems. with electrical conductivity ranging from 10-6 to 10-7 Ω-1 cm-1. a high conductivity of 10-5 Ω-1 cm-1 was measured for the plasma polymers mixed with TCNQ and quinoline. The electronic properties of the plasma polymer were similar to those of semicrystalline poly-p-xylene. The resist properties were improved by including the plasma etching resistive layer in the multilayerd resist system [79]. In 1992. modern electronic applications require films of 30 nm or even thinner. a new system was developed [80] which could plasma polymerise a pinhole-free ultrathin polymer film (2-10 nm) in a RF glow discharge. However. p-Xylene polymer was fabricated by plasma polymerisation and investigated for highfield conduction and photoconduction [72]. 9. PMMA has been used as a plasma-polymerised resist [74. A capacitively coupled RF discharge was initiated in a bos-type reactor in a flow of pure hydrocarbon vapour. 75]. An organic conductive plasma polymer was produced from fumaronitrile and paminobenzonitrile in a heated system [73]. Multilayered resist film was produced by forming alternating multiple layers.

4. The adsorption of urease onto a well-defined solid support. 9. The response time of the capacitance was less than one minute. The adsorption of urease. 9. and with hydroxymethyl (CuPcCH2OH) and phthalimidomethyl substituents [82]. has been achieved to provide the enzymatic hydrolysis of urea. Insulation and packaging materials on implantable electronic devices must be biocompatible. 287 . An NO2 gas sensor was fabricated using plasma polymerisation of copper phthalocyanines. They must have good mechanical durability and good cohesive and adhesive properties. The biological component often used GOD. Plasma-polymerised humidity sensors were proposed using styrene (PPS) [84]. ISFETs are used for pH measurement with a reference field-effect transistor.2 Catalytic Biosensors The most popular catalytic biosensor in clinical analysis is a glucose sensor. 9. The materials processed were copper phthalocyanines without (CuPc) and with a chlorine substituent (CUPc-Cl).12 nm Au sandwich structure.4. It has also been reported that the tetramethyl plasma-polymerised films can be used for sensing propane gas [83].4.1 Enzyme Support Plasma-polymerised HMDSO film was used to produce a biocompatible surface and an enzyme support system [85].Membranes for Electronics 9. The sensor was constructed with a 12 nm Au .8.164 nm PPS .8 Biosensors The promising areas for applying plasma deposition technology to biomedical device fabrication are sensor electrodes and the packaging of implantable integrated sensors. and the activity and stability of the enzyme on the support were studied and optimised. petroleum-based activated charcoal. improving its availability for clinical applications. used in monitoring the blood sugar of diabetes patients.8. to prevent leakage from the implant surroundings. Low temperature plasma polymerisation processes are useful for the integration and show various unique characteristics of the sensors.7 Chemical Sensors Integration of sensors on silicon and/or glass is an emerging technology for fabrication of an intelligent sensing system.4. Sensing elements of the ISFETs were covered by the plasma polymerised styrene and were characterised [81].

the diffusional resistance for the analyte and reaction product is low and a response time of about 4 seconds was obtained. The plasma-polymerised film is an alternative material for the immobilisation matrix that allows for such operation. methacrylic acid and 2-amino-benzotrifluoride was prepared [86]. oxygen and ammonia plasma treatment was carried out to introduce carboxyl and amino groups. and hence. with rejection of interfering compounds. Another sensor using plasma-polymerised films has been reported [87]. The polymerisation condition needed relatively low power discharge. which was fabricated on a silicon substrate. This overcomes the poor adhesion on slide glass or silicon substrates without a chromium layer (often used between a glass slide and platinum to promote adhesion but causes undesirable electrochemical side reactions with alloy formation). GOD is encapsulated between a Millpore membrane filter and a propargyl alcohol plasmapolymerised layer. The pores of the plasma-polymerised matrix are small enough to prevent loss of GOD but large enough to allow the diffusion of glucose and electron. however. This event is primarily an electron transfer process mediated by a specific enzymatic reaction.5-lacton + H2O2 (9. Subsequently. A large amount of GOD was immobilised onto the surface of the film.Handbook of Polymers in Electronics GOD specifically catalyses the oxidation of glucose: D-glucose + O2 D-glucono-1. The calibration curves of the sensor were linear from 0. silver and gold) detects the biochemical reaction event. 288 . 90]. These sensors. Encapsulation of GOD by plasma-polymerised film has also been proposed [89. the denaturisation of GOD frequently caused by the high energy of plasma species was minimised. Nylon membranes have been widely used in such a sensor assembly for conventional applications.05 mmol/l glucose to 2 mmol/l glucose and the variance for a series of 10 injections of 2 mmol/l glucose was found to be 2%. This overcomes the problem with wire electrodes.5 mmol/l glucose to 100 mmol/l glucose and a response time of about 2 seconds was obtained. respectively. The calibration curves of the sensor were linear from 0. The plasma-polymerised films were deposited on the electrode. the distance between the electrode and GOD should be as short as possible.2) An amperometric oxygen electrode or a noble metal electrode (such as platinum. The electrode current increases with an increase in the concentration of glucose. Perfluoroallylphosphonic acid plasma-polymerised film was prepared as a charge rejection membrane [88]. which were coupled to GOD. A plasma-polymerised glucose microsensor using acrylic acid. There have been several typical examples shown in papers. In order to achieve the best sensor performance. The film deposited on a working electrode showed the ability to reject a negative organic interfering material such as ascorbate (vitamin C). Due to the thickness of the film. have slow response times because the thickness of the nylon membranes was more than 50 μm whereas those of the layers of plasma-polymerised films were less than 100 nm. The film also played a role as a barrier for interference from Cu2+. which were found to be difficult to homogeneously coat with Nafion films.

the resonance angle changes. and 38%. the interaction of biomolecule interactions should be carried out close to the gold surface to obtain high sensitivity. Moreover.3 Affinity Biosensors Affinity biosensors take advantage of biomolecular interactions such as antigen-antibody. Since the sensor is often used in seawater.4. It extends from the metal surface into the sample solution. which enabled antibodies to be immobilised on the surface of the film. The values found for coatings made from plasma-polymerised film. respectively. were immobilised onto a piezoelectric device coated with the plasma-polymerised film. A typical penetration depth of the evanescent wave from the gold surface is 289 . Since the evanescent wave decays exponentially as a function of distance. The noise levels of the plasma-polymerised film. Therefore. Affinity biosensors employing QCM are principally based on the measurement of the change in resonant frequency of a QCM according to mass changes on its surface. Standard deviations (sample amount = 10) in the frequency due to antigen-antibody bindings were investigated for three kinds of coating methods. Ethylenediamine plasma-polymerised films formed on gold electrodes covering the surface of quartz crystals are extremely thin and homogeneous. decaying exponentially as a function of distance. The QCM enables one to detect the mass change with a biospecific-binding event. BIAcore (Uppsala. 47%.Membranes for Electronics 9. there are a large number of amino groups. The time-course profile of the sensor response demonstrates a good reusability. collectively referred as ‘biospecific interaction’ in the biochemical and medical field. 54 and 50 Hz. The calibration plot of frequency change against concentration of the antigen. Affinity biosensors using SPR detection have been widely reported [93. and PEI were 5%. Antibodies to the red tide-causing plankton. A surface plasmon wave is a non propagating evanescent wave formed at a metal-coated (mainly gold-coated) surface when light is directed toward the interface at a very specific reflection angle. Therefore. PEI. APTES. respectively [91]. receptor-ligand and nucleic acid base pair association. This indicated that the plasma-polymerised film on QCM was more homogeneous than APTES and PEI. and APTES were 12. They also reported on the ‘red tide’ sensor [92]. sensors produced using this method were more reproducible from sample to sample and exhibited lower noise and higher sensitivity than sensors made using conventional APTES and PEI immobilisation methods. human serum albumin (HSA). Refractive index changes localised near the glass/gold interface resulting from the interaction between biomolecules perturb the evanescent wave and alter the propagation characteristics of the surface plasmon. 94]. Alexandrium affine. Transducers detecting the binding events are mostly quartz crystal microbalances (QCM) and surface plasmon resonance (SPR) devices.8. the plasma-polymerised film matrix played a role as a coating against the seawater. A QCM coated with such a film showed stable oscillation in phosphate buffer saline (PBS) compared with those coated with polyethylenimine (PEI) and (3-aminopropyl) trimethoxysilane (APTES). was linear for concentrations ranging from 10-2 to 10 mg/l with 15 minutes of incubation. Sweden) has developed BIAcore 2000 Biosensor AB into a widely used commercial instrument [95].

carboxylated dextran designed by BIAcore AB. Interface materials between oligonucleotides and substrates need to be well characterised in terms of structural properties such as thickness. 290 . This chip is a high density. Kyong-Hoon Lee for their helpful suggestions. Hitoshi Muguruma for many helpful discussions.Handbook of Polymers in Electronics several hundred nanometres. The sensor chip made with the film showed a better sensor response (higher sensitivity) than a conventional design. Acknowledgements The authors are grateful to Dr.8. The reason is that the antibodies immobilised onto the plasma-polymerised films are two-dimensional and are present at a high density whereas antibodies immobilised onto carboxylated dextran are three-dimensional and are packed at a lower density. Similarly. Plasma-polymerised films might be suitable for the coating matrix between the antibodies and the gold. Plasma-polymerised films and/or the plasma process as an interfacial design between substrates and DNA may thus help towards the increased the use of both biosensors and DNA arrays. DNA array detection systems are widely used. only a few cases have been reported on how such materials are used. Scott J. McNiven and Dr. Due to the demand for immobilising thousands of different kinds of oligonucleotides in mm2 areas. another type of sensor chip was also reported [97] using a plasma-polymerised film and it was shown that it was effective for use in detection of the pesticide. a gene chip has been reported [98]. e. Non specific DNA was avoided due to the thin. Hence. strong adhesion to a variety of materials. the processes for fabricating these chips have employed semiconductor process technology. Miyachi and co-workers deposited a plasmapolymerised film of HMDSO as a support layer for deoxyribonucleic acid (DNA) oligonucleotide arrays [99]. When antibodies are directly immobilised on the gold surface. oligonucleotide probe array for easy detection or identification of genetic information from a virus. etfenprox. chemical resistivity and hydrophobicity. pinhole density. hydrophobic properties of plasma-polymerised film. Recently. The calibration plot of change of resonance angle against concentration of HSA was linear for concentrations ranging from 10-2 to 50 mg/l with 7 minutes of incubation [96].4. antibodies are bound to be denatured and the sensor surface suffers from low surface coverage as well as non specific adsorption..g. it is often difficult to attach a large amount of antibodies with good adhesion. which is a low molecular weight molecule. Therefore. We also acknowledge Dr. 9. the background signal of the DNA array was lower than that of a poly-L-lysine-coated [100] using a conventional interface layer. SPR detection for low weight molecules (molecular weight < 3000) is difficult with conventional sensor chips.4 DNA Sensor In spite of the usefulness of plasma-polymerised film in biosensors.

Nevin. 1994. Morgenstern. 1994. 10. Washington D. 337. 10.A. Biosensors and Bioelectronics. Reactive and Functional Polymers.R.E. Albin. K.P.A. 99. H. Polymer Materials Science and Engineering. Neudeck. 337. 8. 1996. 12. 95. Langmuir. S. 1967. Jagur-Grodzinski. 11. USA. Gregg and A. Hicks. J. 3874. Analytical Chemistry. J. 15. 14. USA. 44. 6. Thin Solid Films. 1993.J. 7. Yoshizawa and J. Kovacs. Surridge. July 1. USA. 485. C. S. L. Nature. Lee. 5. 1996. Hale. 14. Bretz. Sanchez. Allen. Morff and R.Membranes for Electronics References 1. T. Boston. J..J. Roberts. Ed. Geckeker. D. Y. ACS.R. 1994. 1994.C. Analytical Chemistry.. K. Granick. 9. Heller. 16. H.J. Updike and G. 11. Langmuir-Blodgett Films. 1991. Peanasky. ButterworthHeinemann. Skotheim. 291 . 1995. 17. 1990. 407A.T. 1. 1998. 39.W. 1992. 10. Winkels. Arsalani and K. G.S. Hiratsuka. M. Okamoto. MA.A. Chang and G. June 3.. G. Bilitewski.C. ACS. Electrochimica Acta. ACS Symposium Series 556. T. Karan.J. 1994. Journal fur Praktische Chemie/ChemikerZeitung. 3. Schattka and S. 47. 18. 231. Alvarez-Icaza and U. Diebold. Schultze. Cai. 1999.. 986. Ed. 84. D.W. 4. Kendall. Abruna. NY. M. 525A. Petersen and M. Israelachvili. Cosnier. N. J. NATO Advanced Science Institutes Series. 2.W. J. 5970. Karube. Mastrototaro.J. 9. N. Electroanalysis. 246. USA. R. ACS Symposium Series 556. L. Kessel. Johnson. 1847. 1991. 1999. 1999. 443. Saski and I. J. Boguslavsly. P. 263. A.D. E. Tirado. Washington. 322. Physics of Polymer Surfaces and Interfaces. J. 65. 1720. Series C: Mathematical and Physical Series. S. I. 64. R. K. 49. H. 13. S. B. Journal of Physical Chemistry. Hudson. H. Plenum. Maskus.C. New York. D. Science. 214.

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528.W. Rao. Yamabe. Vardhireddy. Hahn. 1803. 62.. 108.K. Ohki. M. F. Tchoubineh. K. Bell and M. 68. 373. ACS. 67. 70. 56. Polymer Chemistry. Tokyo. Japan. 16. 66. DC. Mondin. ACS. 64. 2. 6. Hahn. N. Thomas. F. Proceedings of the ACS Division of Polymeric Materials Science and Engineering. ACS. Journal of Polymer Science. 294 . Part 1. B. 65. T.V. 30.S. 4.M. S. International SAMPE Electronics Conference. M. Proceedings of the ACS Division of Polymeric Materials: Science and Engineering. Yoshida and Y. 1994. NC. 58. DC.L. 8. 27. Sadhir and H. Kashiwagi. Washington. NY. Plenum Press. J. Nakano. 62. 608. 69. USA. 81. Washington. Shibayama and Y.W. Clark and H. Nishio and T. 319. 1991. O. 62. 8. 197. Electrical Engineering in Japan. Eds. 59. Schuessler. Bhide.. 1. 63. USA. DC. 8. F. 1992. Saunders. 1988. Nichols and A. Matsuura. R. P.K. Tyczkowski. Nichols and A. 548. Suleimanova and M.Handbook of Polymers in Electronics 57. Washington. Murayama. Rathbun and P. K. Kerimov. Lee and N.E. Krishnan. Thin Solid Films.I. 1986. Arefi and J. 60. Plasma Polymerisation. Akhmedov. Plasma Processes for Electrical and Electronics Applications. 791. USA. D. 1978. Amouroux.J. Washington. Shen.R. 65. Electrical Insulation Magazine.W. Nakamura.T. 1990. American Chemical Society. USA. 331. M. Suleimanov. Y. ISA Services Inc. 1979. New York. B. Y. 1. 1991. Research Triangle Park. R. Tanaka. 785. 6. T. S. DC. A. Y. Szymanowski. J. Proceedings of the ACS Division of Polymeric Materials: Science and Engineering. IEEE. Synthetic Metals. Bhoraskar and V. Kumar. Proceedings of the 3rd IEEE International Conference on Properties and Applications of Dielectric Materials. S. Polymer Science and Technology. Biomedical Sciences Instrumentation. Kazimierski and H.C. 61. USA. July 1991. 1990. Japanese Journal of Applied Physics.F.A.

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The key attraction of biosensors for the applied sciences is that they offer the prospect of simplified. creatinine. selectivity and sensitivity of sensing devices [1-6]. are on the increase. haemoglobin. Gerard and B. This has led to the development of biosensors. Chaubey. etc. A medical practitioner requires correct information about various biological parameters. agriculture. such as healthcare. etc. wastewater treatment and energy production. agricultural. Industrial applications of biochemical and morphological processes. 16]. petrochemical and pollution monitoring. Malhotra 10. Many companies. With the advent of computerisation and increasing sophistication in many technological areas. preferably on a real-time basis. A common requirement of all these is the need for on-site chemical information on dynamic or rapidly evolving processes. [15. The rest of the market (20%) involves environmental. veterinary medicine and general industrial processing. by providing valuable real-time information [7-12].10 Conducting Polymer-Based Biosensors A. serum. Updike and Hicks described the first functional enzyme electrode based on glucose oxidase deposited onto an oxygen electrode [14]. food manufacturing. albumin. etc. in fields such as production of pharmaceuticals. It is now widely accepted that sensing devices such as biosensors are likely to revolutionise several areas of analytical biotechnology.D. It has been observed that about 80% of the non medical biosensor application market (Figure 10. veterinary medicine. Technical developments of biosensors for medical care have demanded the greatest attention. lactate. There is an increasing demand of biosensors for the determination of substances in biological fluids such as blood. decentralised testing (20%) and consumer testing (5%).1a) is covered by food industries. such as glucose. M. There is a distinct trend in clinical analysis from a centralised laboratory to a doctor’s clinic and to a patient’s self testing at home. urine. Research on biosensors has been motivated by a strong practical instinct with clear applications in sight. dramatic changes are being seen in the way scientific experiments are being controlled. The medical diagnostic biosensor application areas (Figure 10. including MediSense (USA). Clark and Lyons were the first to demonstrate that an enzyme could be integrated into an electrode to construct a biosensor [13]. amylase. urea. defence. virtually non destructive analysis of turbid biological fluids.1b) involve centralised testing (75%).1 Introduction Current research and development in bioanalytical problems aims at improved stability. Boehringer (Germany) and Yellow Springs 297 .

1. Biosensors are analytical devices that respond selectively to analytes in a given sample and convert their 298 . have marketed a hand-operated blood glucose biosensor.1 Biosensors A biosensor is a synergic combination of analytical biochemistry and microelectronics.Handbook of Polymers in Electronics Figure 10. integrated and intelligent devices for biochemical information [17]. This is because development of biosensors is necessary for the realisation of implantable. (b) medical Instrumentation Company (USA). 10.1 The biosensor market: (a) non medical. Biosensors have recently been considered as a highly potential field of scientific research. The National Physical Laboratory (India) has also patented a device that can be used for estimating glucose in blood.

Transduction of the physicochemical effect caused by the interaction with the receptor into an electrical signal. fixed to the carrier materials. The schematic of a biosensor is shown in Figure 10. These include stabilisation of enzymes and retention of enzyme activity for long periods of time.2. which is directly proportional to the concentration of an analyte. In biosensors.1. are used repeatedly. • 299 . 10. and Signal processing and amplification. therefore. the biologically active molecules.2 Schematic of a typical biosensing device comprising of immobilised biomolecule and a transducer respective concentration into an electrical signal via a combination of a biological recognition system and a physicochemical transducer. Biosensors provide a powerful and inexpensive alternative to conventional analytical strategies for assaying chemical species in complex matrices. cells and antibodies. There are several advantages for immobilising the enzymes for application in analytical chemistry.2 Construction of Biosensors In analytical devices. the following sequence of events take place: • • Specific recognition of the analyte. The main aim of a transducer is to produce a continuous or discrete electronic signal. A biosensing device incorporates a biological molecular recognition component connected to a transducer.Conducting Polymer-Based Biosensors Figure 10. such as enzymes. These are.

19]. easily available and more stable.. Figure 10. In the third-generation biosensors (Figure 10. These were based either on the potentiometric or amperometric methods of detection. biosensors can be subdivided into four generations (Figure 10. 21].14]. conducting polymers. The second-generation biosensors (Figure 10. the biocatalyst is either bound to or entrapped between the membranes.3). have been used as the immobilisation matrix [20. In first-generation biosensors (Figure 10.3a). such as polyaniline. polypyrrole. The commercially available kits for estimation of blood glucose are based on amperometry. These biosensors are expected to involve the application of the micro-electrode technology for in-vitro as well as in-vivo applications. The most commonly used matrices are the conducting polymers and silicon.Handbook of Polymers in Electronics Depending on the level of integration.3d) are based on direct incorporation of the biological elements into the matrices [2223].3c). The fourth-generation biosensors (Figure 10.3b) involve the adsorption or covalent fixation of the biologically active component to the transducer surface and permits the elimination of the semipermeable membrane [18. etc.3 Different generations of biosensors (a) first-generation (b) secondgeneration (c) third-generation (d) fourth-generation 300 . These biosensors are found to be cost effective. which in turn are fixed on the surface of the transducer [13.

Immobilisation of the biological component can be done in a number of ways. membranes. Amperometric biosensors measure the current produced during the oxidation or reduction of a product or reactant usually at a constant applied potential. The most common electrochemical transducers being utilised are based on amperometric and potentiometric techniques [26-28]. The biochemical transducer or biocomponent gives the biosensor selectivity or specificity. the excellent specificity of the biological component can be compromised by the partial selectivity of the electrode. Potentiometric biosensors relate electrical potentials to the concentration of analyte by using an ion-selective electrode or a gas-sensing electrode as the physical transducer [29-33]. their immobilisation in a suitable matrix is an important practice in biomedical. tissues. Such sensors have fast response times and good sensitivity. such as polymeric films. thermal.3 Transducers A transducer converts the biochemical signal to an electronic signal. etc. Although the biomolecule incorporated within a biosensor possesses an exquisite level of selectivity. 38]. or some compensation for interfacing signals.1. yeast. gels.4 Biological Component Biocomponents are typically enzymes. A number of matrices have been used for the immobilisation of enzymes on various matrices.1. temperature and ionic strength [36]. etc. This lack of specificity requires sample preparation and separation. antibodies/antigens. Techniques such as physical adsorption. bacteria. cell membrane components. To overcome the problems of slow electron transfer reactions of biological molecules at ordinary electrodes. 25]. 10. The transducer of an electrical device responds in such a way that a signal can be electronically amplified and displayed. [43-46]. The activity also depends on the surface area. industrial and basic enzymology for repetitive and continuous processes.Conducting Polymer-Based Biosensors 10. depending on the type of the component. piezoelectric and surface acoustic wave technology [24. it remains a structurally weak component of the system and is vulnerable to extreme conditions such as pH. 33-35]. gel entrapment. 301 . organelles. porosity and hydrophilic character of the immobilising matrix. For the economic utilisation of the biocatalysts. The physical transducers vary from electrochemical. have large dynamic ranges and are non destructive. [23. The immobilisation of the biological component decreases its activity. crosslinking. These are selective.. carbon and silica. However. liposomes. etc. covalent coupling and electrochemical entrapment. have been used for this purpose [39-42]. but imparts stability to the biological component against the environmental conditions [37. spectroscopic. Most of the biological molecules have a very short lifetime in solution phase and thus have to be fixed in a suitable matrix. The reaction conditions and the methodology chosen for immobilisation are important in determining the activity of biomolecules.

70]. 48]. low energy optical transition. The development of any kind of technology in this field heavily depends on the understanding of the interaction at the molecular level with the biologically active protein. low ionisation potential and high electron affinity. processes which are accompanied by significant changes in conductivity and spectroscopic properties of the films that can be used as a signal for the biochemical reaction [69. The higher values of the electrical conductivity obtained in such organic polymers have led to their being called ‘synthetic metals’. the concept of ‘electrical wiring’ has been reported [67. Conducting polymers contain π-electrons in the backbone and these are responsible for their unusual electronic properties such as electrical conductivity. either as a simple composite or through chemical grafting. 10.Handbook of Polymers in Electronics various modified electrodes have been designed to facilitate direct coupling of biological redox reaction to the electrodes [40. 68]. 302 . 66]. and to modulate the enzyme activity by changing the state of the polymer. 47. The electronic conductivity of conducting polymers changes over several orders of magnitude in response to changes in pH and redox potential of their environment [71]. They can be reversibly doped and undoped electrochemically. The application of conducting polymers in the field of analytical chemistry and biosensing devices has been reviewed by various researchers [43. 48. which can be modified as required. Another advantage offered by conducting polymers is that the electrochemical synthesis allows the direct deposition of the polymer on the electrode surface.5 Importance of Conducting Polymers to Biosensors Conducting polymers have recently evolved as an important research area with diverse scientific problems of fundamental investigations and a potential for commercial exploitation [52-55]. It is thus possible to control the spatial distribution of the immobilised enzymes and the film thickness. it is possible to modulate the required electronic and mechanical properties. Moreover. For efficient relay of electrons from the surface of an electrode to the enzyme active site. 56-58]. while simultaneously trapping the protein molecules [65. Conducting polymers are also known to be compatible with biological molecules in neutral aqueous solutions. These include electrodes modified by deposition of polymer species and electrodes based on conducting salts or conducting polymers [49-51]. the polymer itself can be modified to bind protein molecules [62-64].1. Conducting polymers have attracted much interest as a suitable matrix for the entrapment of enzymes [59. This important development has implications in interdisciplinary research. By chemical modeling and synthesis. The techniques for incorporating enzymes into electrodepositable conducting polymeric films permit the localisation of biologically active molecules on electrodes of any size or geometry and are particularly appropriate for the fabrication of multianalyte amperometric microbiosensors [61]. Electrically conducting polymers have considerable flexibility in the available chemical structure. The electrically conducting polymers contain extended π-conjugated systems with single and double bonds alternating along the polymer chains. Conducting polymers are likely to provide a 3-D electrically conducting structure for this purpose. 60].

80-82]. (c) enzyme directly linked to conducting polymers without any mediator 303 . 73]. conducting polymers can be deposited over defined areas of the electrodes.4 Modes of electron transfer in a conducting polymer-based (CP) amperometric biosensor: (a) enzyme and mediator immobilised on conducting polymer. Numerous published papers conclude that conducting polymers can be used as a medium for the Figure 10. Besides this. Moreover.Conducting Polymer-Based Biosensors Conducting polymers have the ability to efficiently transfer the electric charge produced by the biochemical reaction to the electronic circuit [72. conducting polymers exhibit ion-exchange and size-exclusion properties due to which they are highly sensitive and specific towards the substrate [43. (b) enzyme linked with conducting polymer through mediator. This unique property of conducting polymers along with the possibility of entraping enzymes during electrochemical polymerisation has been exploited for the fabrication of amperometric biosensors [74-79].

Generally. 83. palladium. catalysed by an appropriate enzyme. Metals such as aluminium. PT. 84]. polyazulene. takes place in the bulk of the polymer layer. nickel. platinum and titanium. indium. have been reported in the literature [54. (b) constant potential. to achieve uniform doping and to control the thickness of the film [88]. Polyaniline can be electrochemically grown in the form of a blue-green powdery pigment on a platinum anode during electrolysis of a solution of aniline in sulphuric acid [95-97]. polypyrene. These include PPV. Electrodes should be chosen carefully so that they are not oxidised during the electrochemical oxidation process. which can be either chemical or electrochemical. The methods of electrochemical polymerisation of conducting polymers generally employed are (a) constant current.2 Preparation of Electrodes 10. or galvanostatic. or potentiostatic. properties and applications of PANI. 94]. polyindole.Handbook of Polymers in Electronics immobilisation of enzymes [11. PVCZ. iron and silver are unsuitable for polymerisation of PPy and PT as they will get oxidised before the polymerisation occurs. galvanostatic conditions are employed to obtain thick films. PFu. Polymer films have also been grown on a number of semiconducting materials such as ndoped silicon [90]. In this context many new conducting polymers have been synthesised and studied.1 Synthesis of Conducting Polymers Various methods have been reported in the literature for the synthesis of conducting polymers [85-87]. Metals used successfully as anodes are chromium. gold. PANI and PVCZ. PFu. the most widely used method is oxidative coupling. potentiostatic conditions are recommended to obtain these films. 304 . Many researchers have presented detailed reports on the electropolymerisation mechanism. 43.2. The charge consumption accompanying the rate of polymer formation is linearly dependent on the time and is independent of concentration of monomer. etc. PT. The electrochemical technique has recently gained popularity due to the ease with which it is possible to produce homogenous and coherent films. They provide good detectability and fast response as the redox reaction of the substrate. Since Diaz and co-workers reported the electrochemical synthesis of PPy [93]. gallium arsenide and cadmium sulphide [91] and the semimetal. This chapter provides an overview of the importance of conducting polymers and their application to biosensors. Genies and co-workers have presented a historical survey of PANI [94]. 74. or (c) potential scanning/ cycling or sweeping [89]. 10. A schematic of the different pathways suggested for electron transfer in the conducting polymer-based amperometric biosensors is given in Figure 10. PPy.4. This powdery product was known as ‘aniline black’. Platinum plate and glass coated with a conductive ITO layer are the two most popular electrodes. However.. graphite [92]. such as PANI. many conducting polymers. Details relating to the various methods for the synthesis of conducting polymers have been given in Chapter 13.

1 Methods of Immobilisation Most of the conventional procedures for biomolecule immobilisation (such as crosslinking. 305 .5. However.Conducting Polymer-Based Biosensors 10. Conductivity in conducting polymers is influenced by a variety of factors including polaron length. poly (N-methylpyrrole) [65] and copolymers of N-substituted pyrroles [34]. conducting polymers show enhanced electrical conductivity by several orders of magnitude [98]. 10. 107.2. A few biosensors based on insulating electropolymerised films of polyphenol. PPy and its derivatives play a leading role due to their versatile applicability and the wide variety of molecular (redox) species which may be covalently linked to a pyrrole group. The coalescence of polarons may lead to the formation of bipolarons with increasing charge density. a new concept involving solitons.3 Immobilisation of Biomolecules/Enzymes Stable immobilisation of macromolecular biomolecules on conducting microsurfaces with complete retention of their biological recognition properties is a crucial problem for the commercial development of miniaturised biosensors. Groom and Luong [111] and Ramanathan and co-workers [112] have studied the changes in the dielectric constant in polypyrrole immobilised glucose oxidase films as a function of glucose concentration. polyindole [79]. These are structural deformations produced as a consequence of doping. polarons and bipolarons has been used [99]. Among the conducting polymers. which are energetically non degenerate. 103-106]. Various conducting polymers have been utilised for immobilisation of enzymes at an electrode surface including PPy [7476. At lower concentrations. These defects are delocalised over 4-5 monomeric units and are mobile. Many recent reports have been published on the immobilisation of biological reagents [3. The conduction in PA having two-fold degeneracy has been understood in terms of the motion of charged solitons [100]. PANI [77.2 Conduction Mechanism in Conducting Polymers On doping. 108]. a polaron is envisaged which has a positive charge at one end and a free electron at the other end. resulting in the enhanced conductivity. Bartlett and Caruana [110]. The different methods which can be utilised for immobilisation of the enzyme/biomolecule on conducting polymers are shown in Figure 10. covalent binding and entrapment in gels or a membrane) suffer from low reproducibility and a poor spatially controlled deposition. the conduction occurs via spinless positive charge carriers termed as bipolarons [101]. To explain the electronic phenomenon in these polymeric systems. Malitesta and co-workers [109]. for highly conducting PPy and PT. poly(o-phenylenediamine) and overoxidised polypyrrole have been reported. 10. 113-115].3. the conjugation length and the overall chain length and by the charge transfer to adjacent molecules [102].

This is the simplest method of enzyme immobilisation.1 Physical Adsorption A number of biomolecules have been physically immobilised on conducting polymers [66. 306 . 112.5 Different methods of enzyme immobilisation on conducting polymers (a) physical adsorption (b) crosslinking by bifunctional reagents (c) covalent bonding to the matrix (d) entrapment within the polymer matrix (e) immobilisation in a conducting polymer polyvinyl carbazole (PVCZ) / stearic acid (StA) monolayer using Langmuir-Blodgett film technique 10. etc.3. van der Waals forces. Since the binding forces involved are hydrogen bonds.1.Handbook of Polymers in Electronics Figure 10.. [120] and two-step enzyme adsorption on the bare electrode surface and then on PPy film [121] have also been investigated. 116-119]. The pre-adsorption of an enzyme monolayer prior to the electrodeposition of the polymer. porous conducting polymer surfaces are most commonly used.

which is not reversed by pH or changes in ionic strength.1. In this case.. This is a mild procedure which does not affect the activity of the biomolecules.4 Electrochemical Entrapment A number of enzymes may be incorporated into conducting polymer films during electrochemical deposition on appropriate electrodes. has been utilised to stabilise the biomolecules. 75] and the morphology of the film alters to a more fibrillar form.1.3 Covalent Bonding The biomolecules are attached directly to the matrix by chemical/covalent linkage. Conducting polymers provide a facile means for ensuring proximity between the active site of an enzyme and the conducting surface of the electrode with considerable potential for biosensor construction.2 Crosslinking The crosslinking of the biomolecules via bifunctional reagents.1. 125]. 10. The polymer film can be deposited electrochemically using a potentiostatic or galvanostatic method. e. a solution of the electropolymerisable monomer and the aqueous buffer containing the enzyme is used for the deposition process. a crosslinked network of enzyme is formed resulting in the formation of a bigger molecule on the polymer surface [122. For electrochemical entrapment. This method provides a facile and controllable method for the deposition of biologically active molecules to defined areas on the electrodes.3. However. This method has certain limitations since it may cause a drastic loss in the activity of the biomolecules.3.g. Since chemical modification is involved. Enzymes have also been immobilised on the surface of electrodeposited polymer by applying the bovine serum albumin and glutaraldehyde procedure followed by the electrodeposition of the polymers [1. glutaraldehyde and bovine serum albumin. 124.Conducting Polymer-Based Biosensors 10. It has been established that glucose oxidase can be successfully entrapped in PPy films [74. Covalently attached redox biomolecules on polymers have been utilised as highly electron transfer mediators in flavin adenine dinucleotide (FAD) centres of oxidases [73]. Polymerisation based on the electrochemical oxidation of a given monomer from a solution containing the enzyme is the simplest method of enzyme immobilisation in a polymer at the working electrode surface and results in the formation of conducting or non conducting 307 . it creates a diffusion barrier to the transport of substrate/products in and out of the matrix.3. 123]. this method results in the drastic loss of activity of the enzymes/biomolecules. Carbodiimide coupling to form peptide bonds has been extensively used for the covalent coupling of the enzyme with polymers [126-128]. 10.

107]. The most popular ways to immobilise enzymes on conducting polymers are either to entrap the enzyme within the growing polymeric films [56. 141]. 156]. 134] and multienzyme biosensors [125. During electropolymerisation. covalent binding of an enzyme to a suitably modified polymer with the formation of peptide bonds after carbodiimide activation has widely been utilised [126-128. 130] or can be conjugated with the monomer before polymerisation [131]. 132] used in the preparation of multilayer devices [130. Many theoretical models have been proposed with the electrochemical entrapment of enzyme for the evaluation of the role of the thickness of polymeric layers.3. 148]. 129. the enzyme location. 130. Umana and Waller [74] and Bartlett and Whitaker [77] have described the entrapment of glucose oxidase within the growing network of conducting PPy.5 Immobilisation by the Langmuir-Blodgett Technique It has been observed that the surface of the conducting polymer plays an important role in the effective immobilisation of the desired enzyme. However. This well-controlled procedure of enzyme immobilisation is of great significance in the fabrication of microsensors [107.. Artificial mediators such as ferrocene carboxylic acid or quinones have been utilised to reoxidise the enzymes in conducting polymers [76. etc. 103-104. The Langmuir-Blodgett (LB) technique can be successfully applied to deposit a desired monolayer with the desired orientation of the biomolecules/enzymes [142-145]. This method is inconsistent with the application of an appropriate potential to the working electrode soaked in aqueous solution containing the enzyme and monomer molecules. 10. 152]. the enzyme loading. 139. 153. Ramanathan and co-workers [146] have utilised the polyemeraldine base LB films for the immobilisation of GOD.Handbook of Polymers in Electronics polymer layers containing entrapped enzyme molecules. on the functioning of a biosensor [65. 150]. It has also been observed that the original biocatalyst sensitivity remained unchanged when the electrode surface was renewed after five months of controlled storage [151]. 140. 74. These films have been shown to function as amperometric glucose biosensors and have a linear range from 5 to 50 mM. 155. 135-138].1. 124. 125. The electrochemical entrapment stabilises the enzyme in a polymer layer [149] by protecting against environmental humidity and biological contaminants. The electropolymerisation is often done in aqueous solution at a pH close to neutral in order to immobilise an enzyme without loss of its activity [1. 66. 133. mediators can be immobilised along with an enzyme [107. 308 . Foulds and Lowe [75]. 59. 75. LB films of PT immobilised with GOD and urease have also been prepared for application to respective biosensors [147. 154] or to use a two-step procedure based on the formation of a functionalised conducting polymer film followed by the covalent binding of the enzyme at the functional groups at the polymer surface [125.

These effects are reversible and are caused by variations in the dissociation equilibria of charged groups of the active centre. A partial/complete inactivation of a part of the enzyme molecule may occur (decrease in Vmax). the immobilisation techniques compatible with microelectronic mass production processes will be utilised for the fabrication of amperometric enzyme electrodes. the immobilisation methods must be chosen in such a way that they can achieve a high sensitivity and functional stability.3.4.2 Advantages of Immobilisation Biosensors require highly active enzymes/biomolecules.1 Determination of Enzyme Activity During the course of immobilisation. This is important for economic reasons also. in the future. they are coupled in a complex manner [158]. A non uniform distribution of substrate/product between the enzyme matrix and the surrounding solution affects the measured (approximate) kinetic constants. some portion of an enzyme gets inactivated. the substrate and products are transformed by diffusion.4 Characterisation of Enzyme Electrodes 10. In such a system. • • • • It has been predicted [159] that.Conducting Polymer-Based Biosensors 10. The measurable activity gives an idea about the biocatalytic efficiency of an immobilised enzyme. hydrophobic or other interactions between the enzyme and the matrix (microenvironmental effects) may result in changed Km and Vmax values. i. The following effects have been observed [157] due to the immobilisation process: • A decrease in the affinity of the enzyme to the substrate (increase in Km) is observed due to conformational changes of the enzyme on immobilisation. Therefore.e. The measured reaction rates depend not only on the substrate concentration and the kinetic constants Km (Michaelis Menten constant) and Vmax (maximum velocity of the reaction) but also on the immobilisation effects. the enzyme reaction proceeds in a layer separated from the measuring solution. Ionic. 10. The rate of substrate conversion should rise linearly with enzyme concentration. In biosensors the biocatalyst and the signal transducer are spatially combined.. therefore. Thus diffusion and the enzyme reaction cannot proceed independently of one another. it becomes essential to determine the portion of enzyme remaining active 309 .

One unit can be defined as the amount of enzyme. ∈ is a millimolar extinction coefficient. considerable change in pH activity profile may be observed. which converts 1 μM of reactant into product per minute.Handbook of Polymers in Electronics after immobilisation. These changes will depend partially on the intrinsic catalytic activity of the enzyme and on the substrate concentration. Usually. 310 . A schematic representation of the pH/activity profile of an enzyme (urease) in dilute solution and in the immobilised state in PVCZ films is shown in Figure 10. If the immobilised enzyme is studied in essentially buffer-free conditions. 10.2 Effect of pH It has been observed that the enzymes are active over a limited range of pH and most of the enzymes have a definite optimum pH. the enzymes in dilute solution exhibit a bell-shaped pH activity curve. V is the total volume of assay. s is the surface area of the film and t is the incubation time. With relatively high substrate concentrations. Reactions catalysed by GOD will be low and the internal pH of the matrix will be a bit different from that of the bulk solution. the reaction rate will be high enough to cause a marked difference between the pH of the internal matrix and the bulk phase. the change in pH of a microenvironment of the enzyme will also affect the reaction rate and the increase in substrate concentration. Thus if the bulk phase pH is higher than the optimum pH of the enzyme. The determination of the initial rate of product formation or substrate consumption in the measuring cell using the sensor gives the measure of the enzyme activity taking part in the measuring process. therefore.1) where A is the difference in the absorbance at a particular wavelength before and after incubation. stability may be irreversibly destroyed on either side of the optimum. The pH profile in the linear measuring range of a biosensor is a diffusion controlled phenomenon and. the reaction rate and the rate of H+ liberation for acid releasing reactions. is less sharp than those of the respective enzymes in solution [159] and it shifts towards higher pH in solution due to the decrease in local pH [160]. units per cm2) of the enzyme electrode: U = AV / ∈st (10.4.6. these factors will act synergistically (positive cooperation) or if the bulk phase pH is less than the pH optimum. they will act antagonistically (negative cooperation). The following formula is used to calculate the apparent enzyme activity (U. The optimum pH is obtained due to the effect on the affinity of the enzyme with the substrate. For such a case.

6 Activity profile of an enzyme (urease) in (a) native state (■) and (b) after immobilisation in the polymer matrix (PVCZ) at different pH in phosphate buffer (●) 10. A is a numerical constant. and dissociation of the enzyme-product complex to products and free enzyme. The increase in the enzyme activity with temperature follows the Arrhenius relation: log k = log A .e.Conducting Polymer-Based Biosensors Figure 10. i.3) 311 .303 RT (10. R is the thermodynamic gas constant and T is the temperature (in K). the heat.. free energy and entropy of activation. There are at least 18 thermodynamic parameters for the forward reaction. free energy and entropy of the process for each of these stages.3 Effect of Temperature The overall enzyme-catalysed reaction succeeds in three steps: formation of the enzymesubstrate complex.303 R (10.Ea / 2. Ea is the activation energy. and the heat. conversion of the complex to an enzyme-product complex. The slope of the Arrhenius plot (log k against 1/T) is given by Slope = Ea / 2.2) where k is the reaction rate constant.4.

Handbook of Polymers in Electronics It has been observed that the rate of enzyme reaction rises with temperature up to a certain maximum above which, thermal inactivation of the enzyme takes place. The inactivation of enzymes by heat is due to the denaturation of the enzyme protein. The effect of the instability of the enzyme, free and in the immobilised state, can be studied by exposing the enzyme to thermal treatment for a defined period prior to measuring its activity at a temperature at which it is stable. Chaubey and co-workers obtained 40 °C as the critical temperature of PPy-polyvinyl sulfonate films immobilised with crosslinked lactate dehydrogenase [123]. The activation energies below and above the critical temperature were found to be 93.3 and 22.4 kJ/mole, respectively.

10.4.4 Effect of Storage Time
A biosensor should have excellent stability, reproducibility and a long-term storage time. Biosensors with an electron transfer mechanism based on shuttling of the free diffusing artificial mediators between the enzyme and electrode surface have poor long-term stability due to continuous loss of mediators [163]. In order to increase the long-term stability, it is essential to utilise a new electron transfer pathway between the enzyme and the electrode surface [164]. In this context, conducting polymer based biosensors have been reported to undergo direct electron transfer between the enzyme and the electrode surface [165, 166].

Figure 10.7 Effect of storage time on the response of a conducting polyaniline based lactate biosensor: ■ LOD in solution phase and ■ LOD in immobilised state 312

Conducting Polymer-Based Biosensors It has been observed that enzymes are highly unstable in the solution phase and lose their activity rapidly with time. In the immobilised state, the enzyme is observed to lose its activity very slowly. The immobilisation of enzymes on conducting polymers provides increased stability but decreased electron transfer in the medium resulting in the reduced response of the biosensor. The response of the enzyme lactate oxidase (LOD) to the analyte in solution and in the immobilised state as an enzyme electrode after storing at 4-10 °C is shown in Figure 10.7.

10.4.5 Response Measurements
Use of electropolymerised conducting films in the development of small sensing devices is found to be important because electropolymerisation allows control over the thickness and spatial location of electrode modification. These interfacing electroactive materials have inherent oxidation-reduction abilities. These materials are important for direct and rapid electron transfer at the electrode surface [73, 119, 161-163]. Physical and chemical properties can be modified by appropriate polarisation and doping with counter ions. When a biologically active material interacts with an analyte, a physicochemical change takes place that is converted into an electrical output signal using a suitable transducer. Based on various types of transducers, biosensors may be classified into optical, calorimetric, piezoelectric and electrochemical biosensors. Cooper and Hall have reported the electrochemical response of a GOD loaded PANI film [84]. Mu and co-workers have studied the bioelectrochemical response of the PANI-uricase electrode [162]. The factors affecting the overall response of amperometric biosensors involve current limiting processes. There is a diffusion of substrate from the bulk solution to the outer surface of the membrane, enzyme diffusion of the product through the enzyme layer, and quiescence of the solution (if the enzyme layer is thin). For thick enzyme layers and slower diffusion of substrate through the enzyme layer compared to external mass transfer, simultaneous limitation of higher enzymatic reaction and diffusion must be considered. The electrochemical synthesis of conducting polymers allows the direct deposition of the polymer on the electrode surface, while simultaneously trapping the problem molecule. It is thus possible to control the spatial distribution of the immobilised enzyme and the film thickness, and to modulate the enzyme activity by changing the state of the polymer.

10.5 Types of Biosensors
Based on the type of transducer used, biosensors can be classified as optical, electrochemical (amperometric or potentiometric), piezoelectric or thermal. Among all these the electrochemical biosensors are most widely used. 313

Handbook of Polymers in Electronics

10.5.1 Optical Biosensors
Optical biosensors are based on the measurement of light absorbed or emitted as a consequence of a biochemical reaction. In such biosensors, light waves are guided by means of optical fibres to suitable detectors. Such biosensors have been used for the detection of pH, O2 and CO2. Gerard and co-workers have optically measured the pyruvate concentration (Figure 10.8) by immobilising lactate dehydrogenase (LDH) onto a PANI electrode [163]. These electrodes are stable for about 15 days and have a response time of about 90 seconds. Chaubey and coworkers have immobilised LDH on polypyrrole-polyvinyl sulfonate (PPy-PVS) electrodes on ITO plates and have estimated the lactate concentration by optical measurements [123]. Singhal and co-workers immobilised glucose oxidase on polyhexyl thiophene by the LB technique and fabricated an optical glucose sensor using UV-visible spectroscopy [147]. Urease and glutamate dehydrogenase (GLDH) have been co-immobilised in electrochemically prepared PPy-PVS films for application in a urea biosensor [66]. Quantification of urea by kinetic methods was carried out by measuring the oxidation of NADH in the presence of glutamate dehydrogenase and urease at 350 nm: Urea + H2O → NH4+ + 2HCO3– α-ketoglutarate + NH4+ + NADH → L-glutamate + NAD+ + H2O (10.4) (10.5)

Figure 10.8 Calibration graph of an optical pyruvate biosensor based on polyaniline


Conducting Polymer-Based Biosensors

10.5.2 Electrochemical Biosensors
The interaction between the enzyme and substrate produces an electrochemical signal that can be detected by an electrochemical detector. These are based on mediated or unmediated electrochemistry. Conductometric Biosensors
The conductometric biosensors measure the changes in the conductance of the biological component arising between a pair of metal electrodes. Contractor and co-workers constructed biosensors for glucose/GOD, urea/urease, neutral lipid/lipase and haemoglobin/pepsin by monitoring the change in the electronic conductivity, which is a result of a change in redox potential and/or the pH of the microenvironment in the polymer matrix [167]. The response of a urea conductometric biosensor is shown in Figure 10.9. Ramanathan and co-workers studied the application of polyaniline LB films as glucose biosensors [146]. They have also investigated the dielectric spectroscopic measurements of a PPy/glucose biosensor. Conductivity biosensors based on conducting polymers have been developed for penicillin [168].

Figure 10.9 Response curve of a conductometric urea biosensor Potentiometric Sensors
Potentiometry is a rarely used detection method employed in biosensors, with enzymes immobilised in an electrodeposited polymer layer, although certain advantages over 315

Handbook of Polymers in Electronics amperometric detection for a PPy-based electrode with immobilised GOD have been demonstrated [84]. Potentiometric biosensors with conducting polymers can be produced, using the pH sensitivity of polymers [169]. The sensitivity of PPy to NH3 was used to produce such biosensors [170, 171]. LB films of poly(N-vinyl carbazole) have been utilised for the fabrication of a potentiometric urea biosensor (Figure 10.10). Conducting polypyrrole molecular interfaces have also been used to modulate the biological function of enzymes and living cells at the electrode surface by the adjustment of electrode potentials. Often, additionally obtained discrimination of electrochemical interfaces, by using conducting polymers as matrices for enzymes, allows the use of such biosensors for analysis of natural samples, e.g., flow injection determination of lactate in whole blood. Apart from the advantage of a well-defined formation of the polymer layer, this methodology has some difficulties associated with a significant chemical and electrochemical activity of the polymer matrix due to the similarity of these materials towards ion-exchange processes and redox equilibrium. Karyakin and co-workers have described a potentiometric pH response of electrodes modified with PANI for application as a glucose biosensor [172]. These electrodes exhibit a fully reversible potentiometric response of about 90 mV/pH in the range of pH 3-9. This biosensor has a response of about 5-6 minutes and has been shown to be useful

Figure 10.10 Potentiometric response of PVCZ/urease electrodes with different urea concentration


Conducting Polymer-Based Biosensors for estimation of glucose in the range of 0.1-30 mM. A creatinine electrode was fabricated by co-immobilisation of creatininase, creatinase and sarcosine oxidase in a PPy matrix [173]. Difficulties concerning the immobilisation of enzymes in the electrodeposited polymer layer or the mechanism of the entrapment and dynamics effects on a number of biosensors have been widely discussed. However, no conclusive reports on the comparison of different polymer matrices for immobilisation of the same enzyme are currently available. Amperometric Biosensors
Amperometric biosensors measure the current produced during the oxidation or reduction of a product or reactant usually at a constant applied potential. The most important factor affecting the functioning of amperometric biosensors pertains to the electron transfer between catalytic molecules, usually oxidase or dehydrogenase, and the electrode surface, this transfer most often involving mediation or a conducting polymer. Although the role of the electrodeposited conducting polymer films is not fully understood and explained, various polymers used for the enzyme immobilisation may significantly affect the response of biosensors sensitive to given species. Much work has been done in recent years on the application of electrochemically grown conducting polymer layers in amperometric biosensors. A theoretical model describing the operation of a conducting polymer based biosensor has been reported. In such a model, two different mechanisms have been suggested. An enzymatic reaction may take place at the polymer/solution interface without any diffusion of the substrate molecules into the polymer, or diffusion of substrate into the bulk of the polymer layer due to its porosity may occur [174]. It is shown that the quinone-hydroquinone reaction at a PPy modified electrode is accompanied by the diffusion of the substrate into a porous polymer layer. A general opinion is that no electron transfer occurs between the working electrode surface and the enzyme molecules entrapped in the polymer layer. However, de Taxis du Poet and co-workers have suggested a direct electron transfer between the redox centre of GOD immobilised in poly(N-methylpyrrole) and a gold electrode surface [73]. The immobilisation of GOD via manipulation of pore size in PPy to enhance enzyme loading, has also been reported [175]. Verghese and co-workers have conducted similar experiments in PANI/ GOD films [176]. Biosensors based on conducting polymers have found potential applications in healthcare, veterinary medicine, environmental monitoring, immunosensing, etc.


Handbook of Polymers in Electronics

10.6 Biosensors for Healthcare
10.6.1 Glucose Biosensor
Selective determination of blood glucose is of utmost importance for the screening and treatment of diabetes. About 4% of the world population is presently suffering from diabetes. Normal blood glucose concentration varies from 4.2-5.2 mM. A number of glucose biosensors are available in the market for blood glucose estimation, but none of these is based on conducting polymers. Numerous reports have been published for the immobilisation of GOD in conducting polymers for glucose estimation [75, 110, 175]. GOD catalyses the oxidation of glucose in the following sequence of reactions: D-Glucose + GOD (FAD) → Gluconolactone + GOD (FADH2) GOD (FADH2) + O2 → GOD (FAD) + H2O2 (10.6) (10.7)

Conducting PPy is one of the first conducting polymers to be used for the fabrication of a glucose biosensor [75, 84]. These studies have indicated that up to 125 mU of GOD activity can be incorporated. Umana and co-workers have fabricated a PPy-based glucose biosensor for detection of hydrogen peroxide [74]. The response current of these electrodes was found to be diminished after about one week indicating gradual leaching of the GOD from the PPy matrix. This has been attributed to the electrostatic repulsion between the cationically charged enzyme and the polycationic PPy as well as the porosity of the PPy. It has been investigated if the polymers containing para- and ortho-quinone groups as electron-transfer relay systems for oxido-reductases can effectively catalyse the electrooxidation of glucose [177, 178]. Ramanathan and co-workers have immobilised GOD after manipulation of the pore size in PPy to improve the loading of the enzyme [175]. The incorporation of large size dopant anions such as paratoluene sulfonate (PTS) and ferricyanide into PPy films during electropolymerisation and subsequent exchange of these ions with a smaller ion like chloride in solution, ion self-exchange or electrochemical switching renders the PPy more porous and the immobilisation of GOD more facile. The response of such polypyrrole-GOD electrodes is shown in Figure 10.11. L-B films of polyemeraldine base have been deposited on ITO glass substrates by injecting a solution of 60% CHCl3 in N-methyl phenazine containing 100 μl of GOD. The activity of GOD immobilised in these polyemeraldine base films determined by the o-dianisidine procedure has been found to be 5 IU cm-2 [146]. A few reports are available wherein conducting polymers have been incorporated in materials such as graphite [179] and carbon paste [180]. However, these have not yet been commercialised. A glucose biosensor utilising covalently coupled GOD to poly(o-amino benzoic acid) (PAB, a carboxy group functionalised polyaniline) has been described [42].


Conducting Polymer-Based Biosensors

Figure 10.11 Amperometric response of GOD immobilised PPy based glucose biosensors for PPy-ferricyanide unexchanged (▲) and PPy-ferricyanide exchanged with Cl– (■)

Amperometric response measurements conducted via unmediated and mediated (with ferrocene carboxylic acid and tetrathiafulvaline) reoxidation of GOD have shown that glucose can be detected over a wide range of concentrations. An enzyme-conducting polymermediator model provides for better charge transport in a biosensor. The screen-printed electrodes consisted of two silver tracks with an active working area of 4 mm x 2 mm (Figure 10.12), printed on a polyvinyl chloride (PVC) substrate. On one of the tracks, the Ag/AgCl reference electrode was screen-printed and on the other electrode, the PAB/GOD

Figure 10.12 A two electrode set-up used for an amperometric glucose biosensor based on poly(o-amino benzoic acid). Each electrode consists of two screen-printed tracks of Ag paste. On one of the tracks, Ag/AgCl (reference electrode) was printed and on the other, a PAB/GOD complex was adsorbed (working electrode). The non working area was covered by the PMMA mask.


Handbook of Polymers in Electronics complex was adsorbed. The area of the electrode exposed to the solution was always kept at 8 mm2 by masking it with a PMMA layer. A nylon membrane shielded the working area of the screen-printed PAB/GOD electrode. The optimal response obtained at pH 5.5 at 300 K lies in the range from 1 mM to 40 mM of glucose. The operational stability of the PABbased glucose biosensor has been experimentally determined to be about six days.

10.6.2 Urea Biosensor
Urea is the most important end product of protein degradation in the body. Its concentration in blood depends on the protein catabolism and nutritive protein intake and is regulated by renal excretion. Thus the estimation of blood urea nitrogen is important in the assessment of kidney failure. The normal level of urea ranges from 3.6 mM to 8.9 mM. All enzymatic methods for urea determination are based on the principle of urea hydrolysis by urease: (NH2)2CO + 3H2O → 2 NH4+ + OH- + HCO3– (10.8)

Most biosensors described in the literature for the determination of urea are potentiometric based on NH4+ or HCO3- sensitive electrodes [181, 182]. Osaka and co-workers constructed a highly sensitive and rapid flow injection system for urea analysis with a composite film of electropolymerised inactive PPy and a polyion complex [183]. Pandey and co-workers fabricated a urea biosensor based on immobilised urease on the tip of an ammonia gas electrode (diameter: 10 μm) made from a PPy film coated onto a platinum wire [170]. The enzymatic response was achieved in the wide range of 0.001-0.05 M with a stability of more than 32 days. Cho and co-workers [184] developed a procedure for urea determination by crosslinking urease onto PANI-Nafion composite electrodes, which could sense the ammonium ions efficiently. Such a urea biosensor has a detection limit of about 0.5 μM and a response time of 40 seconds. Immobilisation of urease and glutamate dehydrogenase enzymes in electrochemically prepared PPy/PVS film has been carried out using physical adsorption and electrochemical entrapment techniques [66]. Hydrolysis of urea is catalysed by the enzyme as in Reaction 10.4. The ammonium ion released in the first reaction is coupled with α-ketoglutarate in the presence of GLDH; NADH acts as a cofactor (Reaction 10.5). A kinetic method was utilised for the quantification of urea (Figure 10.13) by measuring the oxidation of NADH in the presence of glutamate dehydrogenase and urease at 350 nm. The leaching was found to be 5%-10% in the case of entrapped enzymes over a period of one hour in solution. However, in the case of adsorbed enzymes, this was found to be 15%-20%. The half-life of this electrode was found to be about 30 days for adsorbed enzymes and 35 days for the entrapped enzymes.


This may lead to a shift of the unfavourable reaction equilibrium by partial trapping of the reduced cofactor. or by using mediators [186] or additional enzymes [119]. Most of the lactate biosensors are based on enzymes like lactate oxidase (LOD) and lactate dehydrogenase (LDH).3 Lactate Biosensor L-lactate is the intermediate product of carbohydrate metabolism. respiratory insufficiencies and heart diseases.Conducting Polymer-Based Biosensors Figure 10. the biochemical reaction has been coupled to the electrode via NADH oxidation. A needle-type lactate biosensor has been recently developed by Yang and coworkers who fabricated poly (1.3-phenylenediamine) electrodes immobilised with LOD for continuous intravascular lactate monitoring [185]. Different lactate oxidising enzymes use different co-substrates and. and finds immense importance in neonatology and sports medicine. In the enzyme electrodes based on LDH. The rapid. 123.4 V. accurate and selective assay of L-lactate and pyruvate is necessary in clinical biology where it is important in the growth of certain cells and in fermenters. 321 .6. L-lactate also plays an important role in food industries engaged in fermentation of wine and dairy products. either directly [119. a variety of electrochemical indicator reactions in biosensors can be utilised.13 Lineweaver-Burke plot for the urea biosensor based on PPy/PVS films adsorbed with urease 10. 163]. The lactate concentration level in blood indicates various pathological states. Direct oxidation of NADH requires potentials of more than 0. including shock. therefore.

1 mM to 1 mM of lactate with a detection limit of 5x10-5 M. The linearity for the LOD/LDH immobilised electrodes has been found to be from 0. Figure 10. Potassium ferricyanide has been extensively used for spontaneous oxidation of NADH in potentiometric LDH electrodes [186].2 V (bias voltage).Handbook of Polymers in Electronics other interfering substances get oxidised at this potential. NAD+ is reduced to NADH as a result of its reaction with L-lactate in the presence of LDH [123]. mediators or pretreatment of the electrode have been utilised. Regeneration of L-lactate by substrate recycling (Figure 10. Yao and co-workers observed that the co-immobilisation of LOD and LDH in poly(1. A comparison of the results obtained with the PANI electrodes immobilised with either LOD or LDH. These enzyme electrodes are stable for about 3 weeks at 4-10 °C implying that these can be used for estimation of L-lactate in cells and fermentation. pH. indicates that the co-immobilisation provides the possibility to detect L-lactate at lower concentrations. In order to avoid this. An attempt has also been made to experimentally investigate the effect of film thickness.2-diaminobenzene) films show a highly sensitive detection of L-lactate due to amplification of the signal by substrate recycling [187]. temperature and enzyme concentration on the activity of the PPy-PVS/LDH electrodes. The PPy-PVS film acts as an electron acceptor and hence gets reduced.14) is shown to provide an amplification of the sensor response. LOD and LDH have been co-immobilised on electrochemically prepared PANI films by physical adsorption [119].14 Substrate recycling of lactate/pyruvate in PANI/LOD-LDH electrodes 322 . Chaubey and co-workers have reported the results relating to the electrochemical preparation and characterisation of the PPy-PVS/LDH electrodes. NADH in turn is oxidised at the working electrode releasing two electrons at 0.

15.15 Response curve for the polypyrrole-ferrocene carboxylic acid based cholesterol biosensor 323 . The sensor response was also found to be independent of the applied potential between –100 and 100 mV.8 V vs SCE (standard calomel electrode) [190]. Kumar and co-workers have used Figure 10.05 mM. cerebral thrombosis and coronary diseases.1 M phosphate buffer containing NaClO4 (10 mM) and 15 to 55 IU/ ml of ChOx at 0.6. The sensor shows high reproducibility in the range 0 to 250 μM with the detection limit of about 5 μM of cholesterol.Conducting Polymer-Based Biosensors 10. Trettnak and co-workers prepared a cholesterol biosensor by electropolymerising pyrrole in solutions of 0. The amperometric cholesterol biosensor based on PPy/ferrocene carboxylic acid electrodes is shown in Figure 10. It was therefore suggested that the sensor response is limited by the interfacial transport or reaction rate of H2O2. In the case of immobilised HRP and ChOx the sensor yields 0. The response was proportional to the cholesterol concentration up to 0.4 Cholesterol Biosensor Cholesterol and its fatty acid esters are important components of nerve and brain cells and are precursors of the biological materials such as bile acids and steroid hormones. Kajiya and co-workers immobilised cholesterol oxidase (ChOx) and ferrocene carboxylate in PPy electrochemically to describe the sensitivity of the resulting films [188].35 μA to 10 mM of cholesterol whereas 3 μA was obtained in the case of free ChOx. Accumulation of cholesterol in blood leads to fatal diseases such as arteriosclerosis. It has been demonstrated that ferrocene attached to polymer chains can mediate electron transfer from horseradish peroxidase (HRP) to a conventional electrode surface [189].

5 DNA Biosensor DNA biosensors are considered to be important for the clinical diagnosis of inherited diseases. rapid detection of pathogenic infections and screening of complementary DNA colonies required in the field of molecular biology research. 195].1 M phosphate buffer (pH 7.4 V in the presence of ferricyanide).11) The oxidation peak at 0. The cyclic voltammetry studies were performed in 0. Ag/AgCl as reference electrode and Pt as the counter electrode. 193].75 V (without ferricyanide) was observed to shift cathodically by about 350 mV (observed at 0. self multiplication. etc. self degradation and self diagnosis. which possess superior intelligent material properties of self assembly. DNA integrated electroactive polymers (thin films or two-dimensional L-B monolayers) have created a novel class of intelligent materials. Introduction of a pyrrole moiety to the 5´ end of the oligonucleotide was explained by phosphoramidite chemistry [197]. Earlier they had described electrochemical copolymerisation of pyrrole and oligonucleotides having a pyrrole moiety. Present methods of genetic analysis are dependent upon the ability to detect specific DNA sequences in a heterogeneous mixture. can be avoided. These ChOx/DBS-PPy/ITO electrodes exhibit a response time of about 60 seconds. linearity from 2 to 8 mM of cholesterol and stability of about three months at 4 °C. More recently. In such a case the oxidation of other elements at 0.0) using enzyme immobilised DBS-PPy/ITO films with and without ferricyanide ion mediator as a working electrode.Handbook of Polymers in Electronics dodecylbenzene sulfonate (DBS) doped PPy films for immobilisation of ChOx by physical adsorption [191].9) (10. Marazza and co-workers have described detection by differential pulse voltammetry and 324 .75 V. Cholesterol + ChOx(ox) → Cholestenone + ChOx(red) ChOx (red) + Fe3+ → ChOx + Fe2+ Fe2+ → Fe3+ + e0. Very few reports related to the interaction of DNA with conducting polymers are available [194. [192. Livache and co-workers have described one-step electrodeposition of a PPy film functionalised by a covalently linked oligonucleotide [196]. self repair. 10.6.4V (10. which could result in an increase in the resulting current. Most of these rely on measuring changes in the peak current of a redox active marker that preferentially binds to the duplex formed in the hybridisation [198].10) (10.

Doping of DNA probes within electropolymerised PPy films and monitoring the current changes provoked by the hybridisation event is another possibility.5 (■). 8.Conducting Polymer-Based Biosensors chronopotentiometric stripping analysis by the use of an electroactive indicator.16). Adsorption on PPy doped with an anion proceeds by anion exchange by the adsorbed molecule. PVS displacement favours strong binding due to energetic interactions with PPy [201]. Possibilities of detecting the signal generated as a result of hybridisation of DNA strands can also be explored. Characterisation of adsorbed DNA on the PPy-PVS films has been carried out by UV-visible spectroscopy.0 (◆). Immobilisation of DNA on a conducting polymer matrix facilitates detection of a signal (amperometric/potentiometric) generated as a result of interaction of proteins or drugs with DNA. 6. as described by Wang and co-workers [200]. Figure 10. daunomycin hydrochloride. DNA possesses a fixed negative charge due to the presence of PO4-. 7. Therefore.0 (▲).16 Adsorption of DNA onto conducting PPy-PVS films as a function of pH.6.0 (● ) on ITO glass plates 325 . Gambhir and co-workers have recently described adsorption characteristics of DNA on electrochemically generated PPy-PVS films as a function of pH. which interacts with the double-stranded DNA [199]. FTIR spectroscopy and cyclic voltammetric studies (Figure 10.

10. Barnett and co-workers have detected thaumatin using antibody containing PPy electrodes [202]. Accurate and efficient monitoring of these residues is therefore of vital concern to the survival of our society. carbazole as a hapten. NO2. Cao and co-workers have reported amperometric gas sensors that can be used for the estimation of gases such as CO. have been fabricated. 10. During the past decade. Yadong and co-workers have performed studies on the ammonia gas sensitive properties and sensing mechanism of PPy [211]. the researchers working in this field of research 326 . The redox enzyme polyphenol oxidase has been utilised to oxidise phenolic compounds in a two-step reaction to the electrochemically reducible quinone [212]. phenolic compounds [207]. Since pesticides remaining in the food crops are transferred through the food chain system. Immunosensors are based on immunochemical principles that can automatically carry out estimation of the desired parameter. In the recent past. Pesticide contamination in developing and developed countries is rapidly growing due to the increasing and indiscriminate use of these organic chemicals in agricultural fields. immunoassays have relied on complex indirect enzyme methods in which the resultant product of the enzyme immuno reaction can be measured [203]. pesticides and industrial pollutants have been developed. which may react to modulate the polymer electrochemistry. viruses. the residues have been cumulatively building up in the human body to alarming proportions necessitating drastic control measures. Recently. portable instruments for analysis of complex fluids and are designed for ease of use by untrained personnel.8 Biosensors for Environmental Monitoring Environmental monitoring of hazardous pollutants has become important to regulatory agencies and the general public. This system has been shown to form the basis of a direct sensor for immunoassay [204].7 Immunosensor Immunosensors are small. Responsive chemoresistors for gas analysis have been reported where the organic polymer modified electrodes were processed by pattern recognition [209. It has been observed by cyclic voltammetry that the reaction of the antiserum influences the polymer matrix electrochemistry by an amperometric response. and O2 [208]. etc.9 Conclusions Marked progress has been made in the last decade towards the application of conducting polymers to biosensors. a number of methods for analysing microorganisms. nitrite [206]. In this context. 210].. antibodies have been raised against the conducting polymer.Handbook of Polymers in Electronics 10. A number of biosensors for environmental pollutants such as sulfite [205]. for rapid assay with sensitivity comparable to that of enzyme linked immunosorbant assay (ELISA).

Bidan. 6. NPL. . Public Health Library Service Microbiology Digest. 1999. 4. M. Analytical Chemistry. 20.Conducting Polymer-Based Biosensors have extensively investigated the immobilisation of enzymes in conducting polymer films. 14. D. 3. Thus conducting polymers are advantageous in the fact that they combine the role of the enzyme entrapment matrix and chemicophysical transducer. S. Electroanalysis. Weetall. The structure of the polymer affects the sensitivity and the detection limit of the biosensor obtained. Simultaneous integration of enzymes and mediators may improve the electron transfer pathway from the active site of enzyme to the electrode. 1984. H. Diamond. 62. 170. Polymer News. for the award of a Senior Research Fellowship. for his interest and constant encouragement. Clarke. 1. 5. Blake-Coleman and S. R.C.J. A. B. The self-assembly of redox enzymes on the surface of an electrode followed by the electrochemical deposition of conducting polymers can be used as a molecular interface to enable the redox enzyme to communicate electronically with the electrodes.M. 6. R.H. 1111. 327 2.C.J.R. References 1. D. It has also been revealed that the conducting polymer matrix serves as an electron shuttling medium between the enzyme and the electrode. A. 1995. 795. Biosensors and Bioelectronics. and is thus capable of functioning as an electron transfer mediator. 237. India. G.V. resulting in substantial miniaturisation and reduced response time. Chaubey gratefully acknowledges CSIR. Sasso. 1992. 1993. Usmani. Yacynych. as well as the ion-exchange and size-exclusion properties leading to improved detection. 45. Functionalised conducting polymers will play an important role in the integration of biological molecules for development of improved biosensing devices. Calder.M.J. 3. Conducting polymers are highly effective in minimising the effect of interferents when used for entrapment of redox enzymes and as protection against electrode fouling by non specific adsorption of high molecular compounds from natural samples. 25. Walla and A. Carr. 1990. Acknowledgements The authors are thankful to the Director.G. Pierce and R. Sensors and Actuators B. 5. Moody.

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K. Ed. Karyakina. Orlov and G. A. Synthetic Metals. ACS Symposium Series 556. 1995. Washington. Journal of the Chemical Society. 1998. Narayanan.D. Analytical Chemistry. Mu.G.H. C. A. H. Kluwer. B. Uchida. 1991. M. M. Analytical Chemistry. 64. New York. Sensors and Actuators B. R. 1999. Wernet. 1237. 1447. 1988.M. DC. 141. 39. 165. Lal and R. B. M. Schmidt. 67. M. S. 7. 1995. Akmal. K. 170. Lukachova. 366. Analyst. R.M. 173. Green and H. 164.G. Mishra.G. Electroanalysis. 257. Verghese. Germany. M. Academic Press. 171. 82. Ohwa and W. 329. Electrochimica Acta. K. 1986. T. Lyons. 1994.C.. C.V. 1993. 172. Nolte. 450. S. Kan and J. Ramanathan.Conducting Polymer-Based Biosensors 159. Sukeerthi.J. Renneberg and F.G. E. USA. Lyons. Chemical Communications. Malhotra. Hill. Fitzgerald and T. USA. 169. 174. C. Eds.L. Bannon. Matsue and I.O.N. Pandey and A. Ramanathan. Ashraf and B. P. L. Analytica Chimica Acta. Guilbault and M. 160. W.S. Schubert in Methods Emzymology. 579. R. Karyakin. 1993. Journal of Applied Polymer Science.A. Ramanathan.J. 175. M. J. 1992. Analyst. 11. Sureshkumar.A. 1994. Mosbach. 161. A. 110.V. 176. 51. Eds. 121.M. 361. 1691. Ratcliffe.C. Schumann in Diagnostic Biosensor Polymers.J. Analytical Communications. 118. 170. Contractor. 13-14. Matuszewski. Lewenstam in Uses of Immobilised Biological Compounds.P. 397. Malhotra.D.J. 2776. 1992.M. 337 . NY.J. Sundaresan and B. Koopal. 167. H. Yamato. C. Szczepanczyk and A. Journal of the Chemical Society. Electroanalysis.M.. Scheller. Usmani and N. 162. 1321. G. 334.R. 166. 36. K. 29. 153. Faraday Transactions I. 1993. N. 239. Chaubey and B. Feiters and R. Nishizawa. De Ruiter and R.Q. W. 1999. M.E. Koopal. 1992. Gerard.. Malhotra. Karpachova.D. A. Zhou. M. 168. Srinivasa. P. Journal of Electroanalytical Chemistry. A. Trojanowicz. Nolte. Dordrecht. Mascini.E.S. T. N. 2642. 1988. S. 113. 1990. F. 163.

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Teoule. C. Analyst. 118. Biosensors and Bioelectronics. Dan. J. Roget. Slater. S.G. 1999. Pearce. G. 1994. 2417.J. R. 402. Marrazza. Pariente. F. 371. Malhotra. Dan. Wallace. 253.. 1993. Bidan and R. S. A. Stetter. Teoule. 379. Gerard. W. 204. R. 201. 14. 210.A. 21.K.G.S. 118. Pande.Conducting Polymer-Based Biosensors 195. Journal of Intelligent Material Systems and Structures. Adeloju. 7.N. Paynter and E. Kazandjian and A. 219. G. Z. USA. 6. S. 286. Jain and B. 212. Wang.Wu. Marx.L. Bartlett and N. 2001. 2000. Journal of the American Chemical Society. D. 1995. 205.O. 5448. Volume I. M. D. Buttner and J. 196. I. 1992. Kamath. O. Mascini. Synthetic Metals. Abruna. Dejean. Sensors and Actuators B. 199.J. Watt.A. G. 2000. 1985. 206. W. E. 1992. Gardner. Hoshimoto. Blair. 2143. Q. 211. 2915.B. 1994. K.R. Shapleigh and H. J.Z. Livache. T. Electroanalysis.A. J. Aantonio and B. G. Tao. 208. 339 . Analytical Letters. Skopec and G. 865. J.N. D. M. Analyst. Dejean. 198. Storrier. Jiang. 200.M. Ed. Barnett. Lim. 71. P. Ito and Y. C. Laing. 4. 27.D.D. Chianella and M. Analytica Chimica Acta. 303. Plenum Publishing Corporation. Ngo. 96. John. G. Yadong. M. Barnett.T.P. S. Klibanov. J. Barthet. C. 207. T. Analytica Chimica Acta.K. 1994. 447. E.J.G. T. Electrochemical Sensors in Immunological Analysis. L. 66. M. S. Analyst.J. Bidan and R. 69.W. A. 5. S. 1997. Electoanalysis. 51. Minehan.D. Wallace and D. 103. 203. Nucleic Acid Research. Mukherjee. Tripathi and D. T. Shaw and G. 22. Gambhir. Porter. Xiangdong and X. 280. Wang. W. A. 1994. Bathet. 1994.M. 197.G. Analytical Chemistry. 107. Wallace. Sadik. 1993. 43. Zhiming. 4856. Journal of Immunoassay. 1997. F. 209. K. 202. R. Friel. 119. Ishimori. J. K. 1999. Kaplan. Cao. Livache.C. Applied Biochemistry and Biotechnology. J. Roget. 1987. Y.

Handbook of Polymers in Electronics 340 .

This is due to the fact that the polymer matrix to some extent prevents interdiffusion of inorganic substituents. the radiative luminescence from these nanoparticles is significantly reduced through non radiative processes mediated by the surface states [6]. In these binary systems.S. nanocrystals prepared using these routes were demonstrated to be useful as fluorescent probes in biological staining and diagnostics [9]. symmetric emission spectrum and are photochemically stable [9]. 8]. which is observed to be a drawback in heterojunction-based inorganic semiconductors. These non radiative losses may be minimised by an improved method of core-shell synthesis [7]. By enclosing a core nanocrystal of one material with a shell of another having a larger bandgap. Narayan 11. The distinctiveness of the nanoparticle properties arises from size-dependent fundamental properties such as ionisation potential. optical fluoroscence and absorbance [1-4]. optical and electronic properties with the degree of interaction between the two components varying from a weak electrostatic interaction to a strong chemical link. one can efficiently confine the excitation to the core. However. Studies of such hybrid systems add further insight into the individual characteristics of the different components. These nanocrystal probes are thus complementary to and in some cases better than existing fluorophores. 341 . when the particle size is smaller than that of the exciton in the bulk semiconductor the lowest energy optical transition significantly increases due to quantum confinement [5]. CdS. In the case of nanoparticles of semiconductors such as cadmium sulphide. Compared with conventional fluorophores. By precisely controlling the size and the surface of a nanocrystal. profound changes are observed in the structural. tunable. In fact. its properties can be tuned.1 Introduction A composite. CdSe. Such nanoparticles when dispersed in a non conductive polymer matrix show improved long-term stability. the nanocrystals have a narrow. a blend or a bilayer consisting of a conjugated semiconducting polymer and a nanoparticle component combine to form an interesting system due to a variety of features. and cadmium selenide. melting point. due to the large surface to volume ratio. The typical range of size for observing variation in these properties depends upon the solid being periodic over a nanometre lengthscale.11 Nanoparticle-Dispersed Semiconducting Polymers for Electronics K. eliminating non radiative relaxation pathways and preventing photochemical degradation [7.

4-phenylene)-block-poly(2. This knowledge is especially required to fully exploit the potential and obtain highly efficient photoactive materials [14.. They have recently been shown to be a viable option for large area display devices and image sensors [10-13]. AmBn. The concept of size-dependent effects has also been investigated in conjugated copolymer heterostructures. PANI and PPy. The tunability of the properties can be achieved by attaching pendant groups to the main chain or by control of conjugation length. length.5benzoxazole) shows quantum confinement effects at room temperature based on PL emission and excitation. i. Conjugated polymers such as PPV. The higher energy gap poly(2. and can be classified as second-generation polymers. The classic model polymers which have been studied extensively from this perspective of electrical transport are polyacetylene. discovered in the 1980s: polyamide 6 342 . PT and their derivatives have been studied for their light-emitting and photodetection properties. the experimental efforts to test these concepts have not shown evidence of such quantum effects. or thickness. exclusively based on polymers without any nanoparticle component [16]. which are periodic copolymers. Recent results have been reported on blends of ABA triblock conjugated copolymer. 15]. it must be mentioned that there has been a large amount of research in the last two decades on nanocomposites of conventional polymers [19]. width. However. Theoretical studies of various aspects of the electronic and excitonic properties of quasi-one-dimensional semiconducting polymer super lattices. Typical of this class of materials is the nanocomposite which researchers at Toyota Co.5-benzoxazole).e. electric field-modulated PL and electric field and picosecond absorption spectroscopy results [16].. Theoretical studies of polydiacetylene-polyacetylene-polydiacetylene triblock polymer chains led to prediction of results similar to those of multiple quantum wells in inorganic low-dimensional semiconductors [17]. have been reported [18]. in the nanometre size range.5-benzoxazole)-block-poly(benzobisthiazole2-hydroxy-1. The electronic structure was systematically studied as a function of copolymer composition and block sizes. There has been considerable effort in estimating the different lengthscales and the timescales of the different photo-induced excitations prior to culmination as free carriers in these polymers. Polymer nanocomposites in this context are generally defined as the combination of a polymer matrix resin and inorganic particles that have at least one dimension. The π (bonding) and π* (antibonding) orbitals form delocalised valence and conduction wavefunctions. Discrete split-off exciton states as well as localisation of electronic states were predicted. poly(2. which support mobile charge carriers. This chapter focuses on the blends and multilayers of a variety of nanoparticles and conjugated polymers. However.Handbook of Polymers in Electronics Conjugated polymers on the other hand derive their semiconducting properties by having delocalised π-electron bonding along the polymer chain.

A few such hybrid materials have been synthesized by Qi and Pickup.1 ns [23]. which provide a platelet reinforcement [19]. A prerequisite for such an enhancement are materials with high electron affinity with a distribution in the polymer matrix such that the interparticle distance is of the order of the exciton diffusion length. was a significant advancement in this field [21. platelets or fibrillar particles would be used. since reinforcement efficiency is related to the aspect ratio (length/diameter. Several benefits of such a nanocomposite that have been identified include: • • • • • • Efficient reinforcement with minimal loss of ductility and impact strength. primarily arising from the constraints in both the yield of free carriers due to the neutral excitation as a dominant species and the low carrier mobility prevailing in these disordered systems. Pristine conjugated polymers with absorption in the visible range do not have good photoconducting properties. with dispersed ion-exchanged montmorillonite as the reinforcement. Improved abrasion resistance. Since this neutral excitation can be dissociated at an interface between the polymer and an electron accepting species. The most extensive research has been performed with layered silicates.Nanoparticle-Dispersed Semiconducting Polymers for Electronics (from caprolactam). Dispersion of electron acceptor nanoparticles such as TiO2 in these second-generation conducting polymers has proven to be an effective methodology for enhancing photoinduced charge separation in a layered device [20]. 22]. Improved gas barrier properties. Heat stability and flame resistance. L/d). The large surface area to volume ratio of the nanoparticle enhances the probability for these charge separation processes. The first-generation conducting polymers have been used as the supporting matrix in different composites for intercalation of catalytically important nanoparticles so that the catalytic activity can be retained in the composite. For maximum reinforcement. the charge separation process must be fast enough to compete with the radiative and non radiative decay pathways of the singlet exciton which is in the range of 100 ps . The blends with conducting polymers go beyond the physical aspects and tap in to the quantum electronic processes. and Residual stress. Reduced shrinkage. Device fabrication with composites of conjugated polymers and C60 as the active layer. charge separation is often facilitated via inclusion of a high electron affinity substance such as C60 [21. with efficient photoinduced charge transfer preventing the initial e-h recombination. 22]. The shapes of the particles used in nanocomposites can be roughly spherical. In addition. and each shape will result in different properties. who have incorporated Pt and PtO in a matrix of 343 . fibrillar or platelets.

such as Fe2O3 containing doped PANI and PPy-silica coated magnetic Fe2O3 particles (5-30 nm) [34]. the conductivity of the composite changes by several orders of magnitude analogous to the metal-insulator transition. while intrinsically conductive polymers are not able to reach the necessary levels of conductivity. However. latex bead and polyethyelene oxide have been fabricated. such as PPy-ZrO2. 11. with the nanoparticle systems of sizes 5 nm and 12 nm having much lower threshold values in terms of relative concentration compared to micronsized nanoparticles [31]. at this stage. Introduction of these insulating particles has shown to increase conductivity in certain cases. The nanocomposites of metal nanoparticles in a matrix of a passive non conducting polymer matrix have a percolation threshold for transport when the nanoparticle concentration reaches values high enough to provide conduction along the chain of connected nanoparticles [30]. PPy-SiO2 and PANI-SiO2 hybrid nanocomposites offer the advantage of a material with large surface area. On the other hand.2 Material Preparation Methods A brief summary of the synthesis adopted for nanoparticles. PPy and PANI nanocomposites using SiO2. insertion of insulating nanoparticles (oxides) in an active conducting polymer matrix also leads to various interesting properties. conjugated polymers and composites is discussed in this section. and PANI-TiO2. very few examples are available regarding the mechanism of electrical transport in the nanocomposites. At the threshold values of the filler concentration. However. These two important characteristics have enabled the above mentioned nanocomposites to be an attractive host for entrapping a substantial amount of metal particles with important catalytic activity and these metal-rich composites can be used for subsequent catalytic application. Intensive efforts are also being made to develop hybrid materials with appreciable magnetic and electrical properties. Metallic levels of conductivity have been achieved in the past by filling polymers with conductive particles (5-10 μm). it has been shown that there are subtle size-dependent percolation thresholds. as postulated recently [27-29]. PPy-Fe2O3. The decrease in the loading density without sacrificing the conductance behaviour of the composite can be achieved if the surface area of the unit weight of the filler is increased. the loadings required for percolation are large enough to seriously compromise the weight and flexibility advantages of polymers. PPy and PANI have the ability to reduce and precipitate some metals from their respective acid solutions.Handbook of Polymers in Electronics PEDOT as the conducting polymer component. The last decade has seen an explosion of activity in 344 . Models based on macroscopic structural rearrangements and packing density have been used to explain these properties. This has been shown to work well as an electrode of a fuel cell and its performance is comparable to the commercial carbon supported catalyst at a higher Pt loading [24-26]. However.

which condenses into liquid molecular clusters.5′ (head to tail). creating a vapour. The issue of structural homogeneity and purity of conjugated polymers becomes particularly important when the target structure is obtained as a difficult to characterise solid. To narrow the particle size distribution resulting from the homogenous nucleation step. of course. More subtle procedures 345 . In this method. This shell contains spacer molecules that prevent the nanoparticles from coming into contact with each other. forming metal oxides. a plasma is used to heat a precursor metal.5′ (tail to tail) [38]. Oxidative coupling of 3-alkyl-substituted thiophenes leaves one with an ambiguity since the coupling can occur in different fashions producing sequences such as 2. The metal atoms in the molecular clusters mix with oxygen atoms. An example which demonstrates these difficulties is the WesslingZimmermann route to synthesise PPV [36. Selectivity is a general concern within chemical synthesis that will. 37]. A homogeneous monodispersion of semiconducting nanocrystallites has been obtained after pyrolysis of organometallic reagents by injection into hot coordinating solvents [35]. Another commonly used application-specific method is discrete particle encapsulation (DPE). A gas is introduced to cool the vapour. which would thus interrupt the π-system. Then a second thin-shell coating is added. raise questions at different levels of sophistication. Surfactants are often used to stabilise the particles. so the nanoparticle will disperse in the best needed format. the molecular clusters are frozen into solid nanoparticles. controlled mixing of Cd2+ with sulfide ions yields colloidal particles of CdS. For metal nanoparticles. Failure to perform this polymer-analogous reaction quantitatively will leave sp3 carbon centres within the chain. such as aluminum oxide. Physical approaches are also used for synthesis of metal oxide nanoparticles. Methods for preparing soluble PPV and PT are standardised to a great extent and are commercially available.2′ (head to head) and 5. No attempt is made to exhaustively cover the various strategies used for fabricating these structures but a few representative examples are provided. The metal atoms boil off. and electrosteric stabilisation for those needing to disperse in a fluid. selected chemicals are used to form a thin polymeric shell around each nanoparticle providing the characteristics a user needs. 2. chemical reduction of metal ions is a common approach. The result is steric stabilisation for nanoparticles in non liquid solvents and polymers. In physical vapour synthesis.Nanoparticle-Dispersed Semiconducting Polymers for Electronics the preparation of various kinds of nanoparticles. the colloidal suspension is typically fractionated using size-selective precipitation. smaller than 100 nm. This method provides discrete nucleation and permits controlled growth of macroscopic quantities of the nanoparticles [35]. where the elimination of small molecules from a so-called precursor polymer leads to a molecular structure with extended conjugation. As the cooling process continues. Common techniques for preparing semiconductor nanoparticles include arrested precipitation of colloidal particles from homogenous solution by controlled release of ions or forced hydrolysis in the presence of surfactants [2-4]. For example.

For example PNVC has been combined with SiO2 to form a nanocomposite in the presence of a polymeric stabiliser. using an appropriate soluble oxidant. For example. A crucial factor in processing films and the hybrid composites is obtaining homogenous solutions before utilising the various options for deposition of these solutions [42]. PVP [43]. PPy is grown within the pores of the respective film supporting the gold particles and the Au-PPy composite grows inside. 346 . Diblock copolymers. spin coating of a nanoparticle with poor dispersion properties in a polymer solution can produce a thin film of small. owing to their ability to form microdomains and to associate in solution in the form of micelles. Since this review essentially focuses on optical and electronic properties and not the structural or chemical aspects of the hybrid nanoparticle-polymer composites. then the hybrid system can be considered to be fairly uniform from the perspective of charge separation strategies. can provide small compartments inside which particles of a finite size can be generated and stabilised [40].Handbook of Polymers in Electronics have been devised to regioselectively synthesise head-to-tail polyalkylthiophenes Many such routes for obtaining high purity polymers with regioregularity are now well established. Gold nanoparticles were arranged within the pores of an Al2O3 membrane using a vacuum filtration technique. Key parameters for the coating are concentration. 11. The template membrane can then be got rid of by dissolving in a solvent [39]. An example of this route for hybrid nanocomposite materials is to polymerise aniline or pyrrole in the presence of some preformed inorganic particles. solvent evaporation rates. Introduction of stabilisers has been known to improve the homogeneity of these systems. it ultimately provides template-free nanocomposite particles. Fe(ClO4)3 is passed through the membrane and encounters rising pyrrole vapour within the membrane. providing an excellent means of formation of such dispersions [40]. Although the work starts with template-guided polymerisation. PPy (colloidal) gold nanocomposites have recently been introduced by Marinakos and others [39]. tubes or wires. PPy-coated gold nanoparticles were also synthesised within the microdomain of a diblock copolymer. Phase separation always exists for multicomponents but if the lengthscale over which this phase separation occurs is more of the order of the relevant lengthscales of the charge carriers/ excitons diffusion processes. Inorganic nanoparticles can be introduced into the matrix of a host conducting polymer either by some suitable chemical route or by an electrochemical incorporation technique. randomly ordered nanoparticle crystallites interspersed with amorphous areas.3 Photophysics of Charge Separation Nanoparticle-Polymer Systems The mechanisms for charge generation and separation upon optical excitation and light emission are different for the spherical nanoparticles and essentially linear chain polymers. the reader is referred to a recent review which exhaustively covers recent efforts from this perspective [41]. and the spinning rates.

On the other hand. it was concluded that photoexcitation of PPV leads to a direct generation of mobile charges through an interband π-π* transition [45. the exciton model requires larger exciton binding energy and extrinsic charge separation mechanisms [47]. The slow component has been modelled in terms of a recombination limited dispersive decay. in spite of large absorption. the capture of oppositely charged carriers (so-called recombination). The evolution of Iph upon photoexcitation and the subsequent decay is. it is argued that the photocurrent (Iph) originates from secondary processes. as shown in Figure 11. 46]. These two points of view differ in two respects. polymer-nanoparticle blend) in a sandwich configuration. Based on the coincidence of the onsets of the photoconductivity and absorption in MEH-PPV. and the radiative decay of the 347 . between a transparent electrode and a metal electrode of suitable work function.Nanoparticle-Dispersed Semiconducting Polymers for Electronics Hybrid systems based on these different class of materials reveal interesting electronic and optical properties and add further insight into the individual characteristics of the different components. Extrinsic mechanisms are most likely to affect the relatively long (>nanosecond) transient photoconductivity measurements [50]. based on a variety of complementary experiments. The photovoltaic properties rely on efficient charge separation upon photoexcitation. Pristine polymers have a problem with large amounts of disorder and low mobilities. where the initial intrachain excitons dissociate to free charges [44]. therefore. A typical configuration for the studies of these properties involves an active layer (polymer. Whereas the band model [45] assumes a small binding energy for photoexcited electron-hole pairs and immediate charge separation. Many of the properties of polymer systems will be examined with three different varieties of nanoparticles: • • • High dielectric.1. EL requires the injection of electrons from one electrode and holes from the other. Exciton dissociation could arise from exciton dissociation at defect sites [48]. The various properties of these systems are explored and provide a glimpse of the richness in terms of photophysical and electronic processes. This relatively slow decay process is interpreted as being extrinsic due to dissociation of polaron pairs (or interchain excitons) through interaction with oxygenated defects to create positive polarons. insulating TiO2. a valuable tool for exploring various processes and developing a deeper understanding of phenomena such as electroluminescence in these systems. Charge generation and charge transport processes have been extensively studied in pristine PPV and its derivatives [44]. exciton interaction with trapped carriers. and Metallic Au. field and thermal ionisation [49]. Semiconducting CdS. or exciton-exciton interaction.

Routes for exciton and charge transfer processes in these mixed systems are shown in Figure 11. the recombination rate and parameters which control the trap-limited transport in these disordered polymer systems. It has been shown that in a nanocrystalline TiO2/PPV composite. as a basis for efficient photovoltaic devices have generated considerable interest [51].2. with the nanoparticles as a sink for electrons. particularly systems of organic dyes adsorbed on TiO2 nanocrystalline films. In most cases. The complementary process of charge separation upon photoexcitation is evaluated on the basis of the charge transport and transfer to the electrodes to constitute a photocurrent. the charge generation efficiency.Handbook of Polymers in Electronics (a) (b) Figure 11.1 TiO2-Conjugated Polymer Composites Studies of charge separation at the interface between organic molecules and nanocrystals.1 Typical device measurement for (a) electroluminescence and (b) photocurrent excited electron–hole state (exciton) produced by this recombination process. Nanocrystalline semiconductor films are highly porous. the polymer acts as the holetransporting medium. Only the first monolayer of adsorbed dye results in efficient electron injection into 348 . the transfer rate. the transit time to the electrodes (which is governed by the transport parameters) and the duration for the decay process for the electron acceptors to come down to an uncharged state. thus having a large internal surface area. excitons photogenerated in the polymer could be dissociated at the interface between the components with the electrons transferred to the nanocrystals [52] (Scheme b in Figure 11. In addition it is normally required to synchronise the charge generation rate. 11.3.2). which depends on the incident photon rate. Considerable attention has been directed towards dye-sensitised nanocrystalline semiconductor films since O’Regan and Grätzel [51] reported a high-efficiency dye-sensitised solar cell.

specific paints. it is necessary to probe the sensitisation of other kinds of dyes. anatase. and exhibits distinct size effects. which has proven to be highly efficient in photon-to-electron conversion. in order to study the photoelectric conversion mechanism and develop a more efficient dye-sensitised solar cell. but the light-harvesting efficiency of a single dye monolayer is very small. and brookite. (c) absorption in the nanoparticle is followed by hole transfer to the polymer [23] the semiconductor. acid-resistant vitreous enamel. which are easily modified [53-55]. followed by the hole transfer to the polymer. Recent work on dye-sensitised solar cells is centred on ruthenium-bipyridine complexes sensitising nanocrystalline TiO2 films. Below a critical size.2 Scheme for efficient charge separation in a nanoparticle-polymer composite (adapted from [13]): (a) absorption in the polymer is followed by an electron transfer process to the nanoparticle (electron acceptor). TiO2 clusters can 349 . However. Anatase TiO2 is used widely for welding-rod coatings. such as organic molecules. ilmenite.Nanoparticle-Dispersed Semiconducting Polymers for Electronics Figure 11. TiO2 particles have been traditionally interesting to study due to a wide variety of applications. etc. thus making light absorption efficient even with only a dye monolayer on each particle. (b) absorption in the polymer is followed by an exciton transfer process to the nanoparticle. the effective surface area can be enhanced about a thousand-fold theoretically. In a mesoporous film consisting of nanometre-sized TiO2 particles. TiO2 occurs as the mineral rutile. octahedrite.

So it is also used to protect against external irradiation and sunlight. TPCs are expected to combine the advantageous properties of conventional PCs with the tunability of such materials as conducting polymers. acts as a charge separator. NLO systems. TiO2 has also been studied for preparation of composites with conducting polymers.2. the photocurrrent spectral response Iph(I) in the reverse bias peaks at the absorption edge. The absorbed organic compounds on TiO2 clusters can be decomposed by oxidation due to the presence of a radical released by irradiation. The high refractive index TiO2 particles can scatter the emitted photons in the active polymer medium such that the gain exceeds loss above a critical excitation threshold. Because of the combination of electrical conductivity of PANI and the UV sensitivity of anatase TiO2. anatase TiO2 nanoclusters have high potential for applications in diverse areas of environmental purification. and under these bias conditions the spectral range of interest should not be a limitation [20. A significant property of nanocrystalline TiO2/PPV composites is that the excitons photogenerated in the polymer could be dissociated at the interface between the components with the electrons transferred to the nanocrystals as shown in Figure 11. 58]. which are structurally similar to those of naturally occurring opals. Another class of application of TiO2 dispersed polymers that has been explored is solidstate polymer laser diodes and photonic crystals. with the primary photogeneration and carrier transport essentially in the polymer backbone. (indicative of an antibatic response) where Iph(I) is 350 .3. The tunable photonic crystals. even in dilute quantities. for solid-state photoelectrochemical devices [56]. photoresponsive materials. Solid-state lasing has been observed from freestanding films of MEH-PPV and TiO2. such as purification of water and air. particularly the width and position of the photonic band gap. The basic PC will be a three-dimensionally periodic array of spherical nanoparticles. such nanoclusters of TiO2 are known as photocatalysts. such as poly(3-methylthiophene) supported on TiO2. Because of the unique properties. Another important aspect which has not been addressed in these devices is that photodiodes are typically used in the reverse bias in the high rectification ratio range for maximum sensitivity. Scattering from the randomly distributed high refractive index nanoparticles greatly increases the pathlength traversed by the emitted light. Conducting organic polymers have been heavily used as the tunable component. consist of periodic particle arrays in which either the particles or a matrix component is either optically or electrically tunable. with greatly reduced threshold pump powers [57]. Therefore. TPCs. TiO2 at such low levels of concentration can be introduced with a fair degree of uniformity in an MEH-PPV matrix as observed in the SEM images shown in Figure 11.Handbook of Polymers in Electronics absorb the energy of UV light to release electrons and radicals by oxidation. In pristine MEH-PPV based devices. TiO2. and photoelectrochemical devices. thereby enabling tunability for the properties of photonic crystals. such nanomaterials are expected to find applications in electrochromic devices. and ferroelectric materials. This feature has been exploited to form efficient photodiodes.

In the case of TiO2 dispersed samples.3 100 nm TiO2 particle uniformly dispersed in matrix of MEH-PPV asymmetric with respect to the absorption response. the spectral features are sensitive to the magnitude of the reverse bias as shown in Figure 11.Nanoparticle-Dispersed Semiconducting Polymers for Electronics Figure 11. the spectral range can be controlled by the magnitude of the bias voltage [20]. With the presence of electron acceptor moieties such as TiO2. barrier depths. The intensity dependence of Iph for input power 0. and this was explained qualitatively on the basis of exciton quenching at the Al interface coupled with the low electron mobility of the polymer. Parameters such as exciton/free carrier diffusion lengths. and film thickness come into play to model the spectra [58]. The open circuit voltage (as shown in the bottom part of Figure 11.4) was in the range of ~0. are in the same order of magnitude as the singlet exciton diffusion length (50 Å-150 Å) observed in MEH-PPV [58].8 V with a short circuit current density of ~5 nA/cm2 for a photon density of 10 μW/cm2. 351 .1 μW/ cm2 to 1 mW/cm2 is linear in the entire voltage range. An Iph/Idark (photocurrent/dark current) ratio as high as 104 at a reverse bias of –4. At higher absorption. λ < 3400 Å.4.5 V and a responsivity of ~50 mA/W at –9 V with a dark current of 10 nA has been observed in these blended materials [23]. there may be a hole transfer process onto the polymer from TiO2. where e-h pairs are generated in TiO2 nanocrystallites. with practically no photocurrent in the absorbing region. The results also highlight important differences in the switching response of the devices in the forward and reverse bias and its implication in photodetector devices [20]. TiO2 nanoparticles play the role of electron acceptors since the interparticle distances. with large surface area.

(b) Typical photodiode characteristic Iph – V. and the barrier width. are the thickness of the polymer layer. which may decide the spectral width of the different regions. 1/β.Handbook of Polymers in Electronics (a) (b) Figure 11. The bias dependendency of Iph(λ) can be qualitatively understood in terms of the model by Ghosh and others [59]: l I ph ∝ ∫0− l b ae ( − ax )e − β( l − l b − x ) dx + ∫ll− l ae ( − ax )dx . l. lb.3V is scaled down by a factor of 10. with Iph measured using the lock-in technique.4 (a) Spectral response of TiO2 dispersed in MEH-PPV in forward and reverse bias. the exciton/free carrier diffusion length. Note that the response at –3. b 352 . 1/α(λ) where α(λ) is the absorption coefficient. The lengthscales of the device.

2´. It was found that the work function of the nanoparticles could be matched with that of the metal contacts improving the electron injection efficiency and it was also observed that the emission colour governed by the 353 . such as CdS. Reports on a heterostructure device with an inorganic layer of CdS and a polymer light emitter show the advantage of the high charge transporting properties of an inorganic semiconductor and the enhanced emission efficiency of the polymer emitter [62].5a. 2. This argument is also applicable for excitons which diffuse and undergo dissociation. TiO2 can also be introduced as a porous nanocrystalline layer into which the polymer penetrates. have also been demonstrated as active layers for emission and detection devices with the optical range of interest tuned by size selection of the nanoparticles. The barrier normally in these sandwich devices is primarily at the metalpolymer interface and is estimated to be ~200 Å [58].9´-spirobifluorine. A clear systematic blue shift in the photocurrent onset with the decrease in the particle size has been observed. Host polymers with different HOMO levels have been used to prove that the Iph enhancement requires hole transfer from the dye to the polymer [55].7´-tetrakis(N. An improvement in processing methods whereby a higher concentration of nanoparticles can be dispersed in the polymer matrix without a phase separation could lead to the realisation of the full potential of these systems for attractive technological applications. a heterojunction of dye-sensitised TiO2 with an amorphous organic hole transport material. the ITO side.3. CdSe and ZnSe. has been demonstrated to be an efficient solar cell with a high yield of 33% [60].7. 11. see Figure 11. The dye-sensitised layer acts effectively as an intermediary for the charge transfer processes. i. Dye-sensitised TiO2 particles blended with different hole-transporting polymer matrices have also been investigated [55]. The nanoparticle has shown to reveal efficient photocurrent [61] and EL properties with the spectral response governed by the particle size.2 Nanoparticle Semiconductors-Polymer Systems Semiconductor nanoclusters.Nanoparticle-Dispersed Semiconducting Polymers for Electronics Iph in this model depends on the ability of the minority carriers (electrons generated in the bulk) to reach (diffuse) the interface and is characterised essentially in terms of 1/β and lb. The forward-bias currents and open-circuit voltages are determined by the conduction band energy of TiO2 [53].e. It is seen that the experimental Iph(λ) at different voltages in the reverse bias can be explained by the diffusion length having a stronger dependency on the voltage than the barrier length within the framework of this model. Iph results in an antibatic response.N-di-p-methoxyphenyl-amine)9. A monolayer of TiO2 can be self-assembled onto the ITO surface using activation of the ITO surface with 3-aminopropyltriethoxysilane [53]. Apart from a single-layer film containing dispersed TiO 2 particles. the numerical estimates of Iph(λ) for different diffusion length yield profiles which are remarkably similar to the experimental results [20]. For illumination from the side opposite the barrier..

Results on such hybrid devices. a maximum at 6200 Å. were reported [63]. At low voltages. respectively. where windows for the detection and emission can be selected by nanoparticle-size engineering and/or modifying the chemical structure of the polymer. and 5250 Å for CdS-44/P3HT (polyhexylthiopene). The EL response of such hybrid devices can essentially highlight the emissive polymer component. CdS-44/MEH-PPV and CdS-44/6FPBO (6-fluoro poly(benzoxazolebioxydecyl)) devices. PC properties of the inorganic component and the EL properties of the polymer in a single device was explored recently [63]. The potential of such devices. for example. and (b) Typical electroluminescence response of 6FPBO and MEH-PPV recombination zone could be controlled by the magnitude of external voltage.) The EL spectra of 354 . where photoconductivity characteristics are dominated by the quantum size of the inorganic semiconductor and the enhanced EL spectral feature is attributable predominantly to the polymer component. was demonstrated [63]. emission from the nanoparticle layer occurs.5 (a) Nanoparticle photocurrent spectral response for different particle sizes. 5400 Å. The possibility of synergistically combining the efficient photoconducting.Handbook of Polymers in Electronics (a) (b) Figure 11. (CdS-44 = 44Å CdS nanoparticle. and at higher voltages the emission from the polymer was reported to predominate [62].

The recombination in the 6FPBO device is closer to the 6FPBO-hole injecting layer interface with a minimum trap emission contribution from the nanocluster layer. The EL efficiency can also be enhanced by optimising device parameters. It has been observed in LED devices based on nanocrystals. The external zero bias photocurrent efficiency in all the hybrid devices is in a similar range as that of pure nanoparticle devices with a responsivity of ~100 mA/W.6.5b. The polymer signature is observed in the photocurrent. 65]. which have high band-edge PL yield. but the Iph(λ) in the non absorbing region of CdS-44 and absorbing region of the polymer is less than 3-4 orders in magnitude than the Iph(λ) in the CdS-44 absorption region. 65]. the possibility of Förster tranfer of the exciton to the nanoparticles will be effective only at the interface leading to a possible emission quenching. to have radiative recombination away from the interface [63. that the insertion of a hole transporting polymer layer enhances the nanocrystal band-edge emission characteristics [62]. charge separation and transport in nanocrystal CdS-44/MEH-PPV composite blends have been studied in detail [23. In the present case the results can be interpreted in terms of the CdS-44 layer enhancing the polymer emission characteristics.6 with efficiency nearly an order of magnitude higher than CdS-only devices and polymer-only devices. Initial results on PL with excitation energies corresponding to that of the polymer in CdS-44/P3HT do not show substantial quenching effects. such as thickness. resulting in a sharper emission. The results correlate quenching with improved quantum yield for charge separation. The large photocurrent primarily reflects the high efficiencies commonly observed in CdS-based detectors due to high absorption and efficient charge carrier 355 . The Iph(λ) and EL response of the CdS-44/P3HT device is shown in Figure 11. The EL spectra in the multilayer hybrid devices are closer to the pure polymer responses as shown in Figure 11.Nanoparticle-Dispersed Semiconducting Polymers for Electronics the pure polymer devices are shown in Figure 11. by choosing polymers of appropriate electron affinity values and by using suitable capping materials for the nanocrystals. with prior information on values of mobility and electron-hole pair diffusion length. It is expected that the absorbance and the emission from the polymer layer will modulate the emission from the CdS-44 layer. In stark contrast. The issues of PL quenching. In the present case of bilayers with completely segregated phases.6. the short circuit photocurrent spectral response in all the three devices is identical to that of a CdS-44 layer independent of the type of the polymer. A significant separation width of nearly 2000 Å (2. Quenching effects can be minimised by reducing Förster transfer rates.0 eV) in the visible range between the emission maxima and the photocurrent region is observed for the CdS-44/P3HT device as shown in Figure 11.5 and Figure 11. It is expected that if the polymer thickness is increased to be comparable to the absorption depth. 6FPBO is an electron transporting emitter [64] while MEHPPV and P3HT are predominantly hole transporting. The Iph(λ) response shown is representative of any CdS-44-based hybrid devices while the EL(λ) response is representative of any P3HT based hybrid device. the spectral response would be modified.

4 nm.6 Depiction of a bifunctional device with a spectral window for detection and emission controlled by independent components with photocurrent and EL of a multilayer device ITO/PVCZ/P3HT/CdS/A1: The nanoparticle size is 4.Handbook of Polymers in Electronics Figure 11. 356 . which corresponds to a band edge of ~450 nm.

The tunability of a Shottky diode based on a semiconductor/conjugated polymer (doped) interface has been explored electrochemically manipulating the work function of the conjugated polymer [66]. A general rule of thumb. In the above case. display electronic. quantum efficiency up to 12% has been reported [64]. Reports on blends of gold nanoparticles and conducting oligomers have demonstrated concepts such as the construction of mesoscopic oligomer bridges between metal nanoparticles [68]. the work function along with the charge carrier concentration and the nature of interface decide the LED characteristics.Nanoparticle-Dispersed Semiconducting Polymers for Electronics separation. Results similar to that of the TiO2 dispersed MEH-PPV have also been observed for CdSe dispersed in MEH-PPV [23. Another concept that has been explored is that of ‘diffused’ and ‘fractal’ p-n junctions in nanoparticle-polymer composites with both p. where both the nanocrystals and polymer components provide continuous pathways to the electrodes.3. One can obtain an area consisting of pure p-type and pure n-type particles close to the electrodes. In this case.3 Gold-Polythiophene Blends Another class of materials. Hybrid systems comprising of these materials reveal several interesting features. alkanethiol-stabilised metal nanoparticles. where Upolymer is the binding energy of the singlet exciton on the polymer and Vcharge transfer is the coulombic energy associated with attraction between the electron and hole in the final. Results have shown that the electron affinity of even the smallest CdSe nanocrystals is sufficient to allow electron transfer from MEHPPV. is Eananocrystal – Eapolymer > Upolymer – Vcharge transfer. with an intermixed region inbetween the electrodes. optical and structural features that are tunable via particle size [67]. a clear case of PL quenching is also observed as an evidence of charge transfer. charge separated state.and n-type nanoparticles.6. Peculiar effects are observed in the intermixed layers since the nanoparticles sizes are similar or smaller than the Debye screening length [30. Diffused junctions are obtained upon converting p-type particles into n-type. The theme of this section is to demonstrate the effects of interfacial chemistry and material heterogeneity on electronic and optical properties of luminescent conjugated polymers at metal interfaces. At high concentration of the nanocrystals. The 357 . Gold nanoparticles have surface reactivity amenable to immobilisation at chemically functionalised surfaces and can bind to positively charged polymers via electrostatic interaction [69] or covalently to amine. 64]. 31]. 11. The novelty of such a dual functional bilayer device with independent control of spectral windows for emission and detection response is depicted in Figure 11. thiol and phosphine functional groups [70]. which has been followed to enhance transfer process.

The different component-specific features present in the film can be distinguished by the contrasting PL properties along with the direct TEM observation of the nanoparticles. a blue shift of ~120 nm in the fluorescence is observed. The shear-force feedback technique in NSOM provides a topographic image in parallel with the optical image. NSOM is used to acquire spectra from regions of size less than that of the wavelength of the light source employed and the results demonstrate the capability of this technique to differentiate the components in the sub-micron lengthscale of these multiphase systems. The circular features are essentially a signature of the Figure 11. see Figure 11.7 Confocal fluorescence microscope image of gold nanoparticles dispersed in P3OT 358 . At the periphery of the fluorescent centres. 72]. Au-P3OT (polyoctylthiophene) systems can be viewed as model systems for probing using NSOM due to the spatial gradient of the spectral shifts occurring at nanometre lengthscales. tunable via the gold nanoparticle concentration. Fluorescence centres of ~1 μm diameter. Randomly distributed circular features with sharp intensity contrast are present throughout the film.7. containing the pure polymer. The striking features in this case are the complex structures that spontaneously appear upon film formation of gold nanoparticles and thiophene-based polymers [71. The source of the PL in the polymer region is known to arise from the radiative decay of the intrachain singlet exciton level. indicating distinct phases.Handbook of Polymers in Electronics electronic structure of the polymer chains is also expected to be strongly perturbed in an environment of these metal nanoparticles. are dispersed throughout the film. with TEM for morphological studies of the phase separated system. In fact. Fluorescence microscopy and near-field scanning optical microscopy (NSOM) have been used to study the PL variation.7. A typical confocal fluorescence image of the Au-P3OT blended film is shown in Figure 11.

As the proportion of polymer is increased.7 and Figure 11.8 are obtained only with polythiophene derivatives. It is also to be noted that these polymer/Au nanoparticle film patterns. such as (a) (b) Figure 11.8 NSOM fluorescence contrast image (1 μm x 1 μm) of a bright spot/sphere on the Au blended P3OT film (a) along with the emission spectra at different distances away from the centre of the spot (b) 359 . The emission of these circular regions resembled the emission from a pristine polymer film which has a PL maximum centred at ~700 nm. NSOM fluorescence images are consistent with the simultaneously obtained topographic image for these PT/gold nanoparticle films. resulting in the creation of local domains. the size of the circular regions increases and the contrast between the bright and dark regions decreases.Nanoparticle-Dispersed Semiconducting Polymers for Electronics differences in the evaporation/dewetting rates of the two systems during the film formation. as shown in Figure 11.

a change in structure and the dependence of topology on interconnected chains.4 Summary In summary. switching speed and substrate choices. These disordered systems are generally parameterised by the presence of a percolation threshold. The origin of these properties is distinctly different in the two components.8. nanoparticles and polymers can form two distinct components in a composite with a diverse set of properties. Spectra are blue-shifted as the tip moved from the centre towards the periphery. The high density of the nanoparticles in the periphery can be explained by the non uniform evaporation rate and a finite mobility of the nanoparticles. weak metal-polymer interaction as the driving factor for the appearance of different phases [72]. giving rise to the inhomogenous radial distribution of the nanoparticles. Another factor which comes into play is the aggregation of polymer chains. An important issue which needs to be resolved is the determination of whether the electronic structural changes of the polymer in the blended system are secondary effects caused by a nanoparticle-induced physical process such as rearrangement of the polymer chains or by a nanoparticle-specific. Spatially-resolved PL spectra are obtained with the fibre tip held at several positions in the vicinity of a typical fluorescent centre of the blended system [72]. 360 . 11. which get pinned at the rim. The ringlike structures have been observed in alkanethiol-coated gold nanoparticles [74]. One can tailor properties in composites by exploiting the various attributes. The PPV-based polymers such as MEH-PPV do not show such distinct phase formation. The PL from these fluorescent centres can be interpreted in terms of a crystalline (maximum ~700 nm) and an amorphous phase (maximum ~565 nm) of the polymer. The nanoparticle mobility in that case was high enough to allow most particles to accumulate in the ring during the receding process of the contact line created by the interface between the solvent and the substrate [74]. In terms of optoelectronic properties. which can act as an effective drag on the nanoparticle motion during the drying process. such as spectral distribution. Nanoparticle-polymer composites demonstrate a synergistic approach to enhance efficiency in a variety of phenomena and in certain instances to achieve a complete set of novel properties. It is noted that a typical nanoparticle stochastically dispersed in a polymer forms a system which is disordered. The emission spectra from different regions are shown in Figure 11.Handbook of Polymers in Electronics P3OT and P3HT. The macrophase separation of these nanoparticles and the polymer in the films arises due to the non formation of a homogenous solution. Considerable efforts to sort out issues such as processibility and stability should lead to the use of such combinations of materials as potential routes to many nanotechnology-based device applications. a far wider range of control and better functionality. the entire advantages of amorphous silicon technology are applicable here with a much greater flexibility.

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S. Schlamp and A. 395. L.A. Brock. W. 1997. Chemical Physics Letters. Gratzel. Applied Physics Letters. Physical Review B. Sarma. A.-H. Applied Physics Letters. Ulanski. Bullot.. 1145. 354.W. J.J. 230.H. M. 6915.A. Bach. Alivisatos.C. 1996. 262. J.S. K.L. Micaroni. Ghosh. Salafsky. 140. Gruner and G. Nature. S. I. 59. Ed. Journal of Applied Physics. 297. Feng. 4. J. 49. 1999. 44. Schropp. World Scientific Publishers. O’Regan and M. 52. Lefrant and J. Narayan. Nanda. H.G. U. U. Gazotti and M-A. 1998. 11. 56.H. B. Scherf. N. 1997. A. Wery. Samuel. J. Physical Review B.P. J. Nanda and D.K. B. 55. Lupo. W. J. R. B. 1998. G. Arango. 16. Nature. Applied Physics Letters.L. De Paoli. Salbeck. Spencer. 290. 53. Neher. 12.D. 1.S. Manoj. Gailberger and H. Colvin. D.E. 54. 1991. Sarma. A. Nogueira. I.F. 1974. Scott and P. M. 71. Weissortel. 9118. V. Electrochemistry Communications. 1999.F. Shaw and C. Bassler.A. 57. 1998. Kuruvilla. 12. K.C. M. H. Moser. Dulieu.J. Applied Physics Letters. Glowacki.K. 74. 57. G. 4. 7831. 55.J. 60.C. 737. Rumbles and R. F. D. 871.C. Journal of Applied Physics. B. 50. 1998. Nature. S. 1997. P. Comte. Daubler. 8643.J. Diaz-Garcia and A. Morel. 58. 61. Brock. Lubberhuizen and R. Sariciftci.A. 12. 62. Heeger. Spreitzer and M. 74. 45. Murthy and D.C. S. J. 72. Hide. Carter and P. 51. T. 63. 353.I. 6. J. 15. 1335. F.L.G. Harrison. Friend in Primary Photoexcitations in Conjugated Polymers: Molecular Excitons versus Semiconductor Band Model. J.D. Chemical Physics Letters. 1991. Singapore. Schwartz. 424. 9.Handbook of Polymers in Electronics 48. 7. 1994.D. 370. A. 1999. Physical Review B.E. Horhold and D. Gratzel. Rowe. 1999. 364 . 583. 256.S. 86. T.W. Carter. J.A. Narayan. 1698.

Taylor. Grabar.J.A. Bright. Jackson.A. J. Lonergan. 1997. Ohara. Gelbart. Freeman. 4. 1998.C.R. 1997.C. 543. G. Narayan. 69. 10. 2. 67. 1992. Novak. V. 77. A. 1629.C. Chemical Physics Letters. R. White. 59.Nanoparticle-Dispersed Semiconducting Polymers for Electronics 64. 36. U. K. R. 678. Springer Series in Materials Science-2502. Sarathy. Marti. Brunner. 73. 65. Allison. Angewandte Chemie International Edition. J. P. P. 2103. Feldheim.J. 2000. Marinakos and D. 5346.S. 11. D. O.S. 97. L. 267. M. Advanced Materials. Ginger and N. G. 447. 68.P. Vijaya Sarathy and K. Du. Smith. Optical Properties of Metal Clusters. 278.M. 6. M.J.G. J.O. Chemical Reviews. 66.G. 135. 74. S. 1995.M. K. Heath and W. 1997. Rienhardt and J. 1999. 1999. Walter and M.M. Synthetic Metals. 10622. Current Science India. 365 . D. Burkett. Spry. Bietsch. 6. 2. Kim and J. 16. 318.S. B. R.L. Ferguson. R. Hollricher and O. Brousseau. 70. M. 1769. Science. Schmid. 72. 1999. Vollmer. K. Science. B. Narayan.C. K.A. 68. Natan. Kreibig and M. 1078. Alexander. Grayson. 1995. C. III. 1709. 71.C. J. Greenham. Review of Scientific Instruments.C. Physical Review B. J. Davis.

Handbook of Polymers in Electronics 366 .

H. at the beginning of this chapter. • • It is noteworthy here. Whilst certainly taking the limelight. refinements in photoresist technology have had to keep pace [8-9]. and The information technology revolution that has seen the enormous increase in the numbers of computer monitors. However. The insatiable consumer demand for ever-increasing visual display quality. lightweight. have seen enormous developments in the use of organic materials that can process electric charge or photons [1-4]. This has arisen as a result of three main factors: The global research effort towards the realisation of cheap. to mention the awful truth about light-emitting polymers – their discovery was entirely serendipitous! Whilst measuring the breakdown voltage of a conjugated polymer [5]. Richardson 12. and in particular the last decade.1 Introduction Electronics at the beginning of the third millennium is still massively dominated by traditional inorganic semiconductors. researchers noticed the emission of faint green light from their device. mobile phones and paging devices in the last 5 years alone. More surprising still. flat-panel. So was born the modern era of organic electroluminescence. However. the real excitement will begin in the next decade or two when polymer transistors become commonplace. As device feature size has gradually decreased since the invention of the first transistor. the last 20 years. luminescent organic compounds are by no means the only group of materials that are continuing to attract research interest in electronics and photonics. metals and ceramics. In one area at least. that of electroluminescent light-emitting diodes. flexible. This is the shy. perhaps. low power displays. The most used organic component in the electronics industry has been around for several decades already: the humble polymer photoresist [7]. is the fact that organic electroluminescence was actually first observed as early as 1963 in single crystals of anthracene [6]. and when these transistors eventually comprise only a few tens of molecules! In a world in 367 . organic materials are poised to make a huge impact on consumer electronics. retiring partner that is essential for the success of every integrated device in every circuit board.12 • Polymers for Electronics T.

Such devices contain several layers of organic materials interspersed between a metal cathode and a transparent (most often ITO) electrode to allow the luminescence to exit the device.1. Arguably the most important breakthrough in organic LEDs came in 1987 when Tang and co-workers [12] used monopolar charge transporting layers alone or either side of an emitter layer.g. not to mention the recent arm transplants. lap-top computers. livers and kidneys.g.. Thus holes were being favourably injected at one side of the polymer and electrons from the metal contact. 12.. Whilst studying the insulating properties of the polymer in an Al-polymer-Al device configuration.2 Polymer Electroluminescence Liquid crystal materials [10] currently dominate the electronic display market since they are cheap and easy to produce and are extremely reliable passive devices. as depicted in Figure 12. researchers at Cambridge made the serendipitous discovery that the conjugated polymer PPV was electroluminescent. wristwatches. and the research field of polymer electroluminescence was born [17]! 368 . bulletin boards). It is less meaningful to discuss complex theories and device designs without devoting some thought to the deposition techniques available for the fabrication of polymer membranes for electronics devices. their brightness effectively is dependent on ambient lighting conditions (except for slight enhancements made possible with backlighting). because they process incident light from the surroundings. This chapter will include an introduction to some of the topics mentioned above with the intention of giving the reader some insight into the world of molecular electronics. lowvoltage displays with an improved brightness and viewing angle dependence over liquid crystal displays. video camera displays). the idea of molecular-scale transistors and other devices is really not far-fetched. they noticed green light emerging from the device. They produce no light of their own but utilise ambient light that is reflected from the displays in which they are housed.Handbook of Polymers in Electronics which a surgeon can transplant hearts. Radiative recombination was occurring within the PPV. Ordered polymer layers of well-defined thickness and orientation do not appear by magic and so this chapter is closed with a survey of the fabrication technologies at the disposal of the organic device engineer. Whilst such displays are extremely effective in a wide range of singleuser applications (e. Although much of the early organic LED work focused on low molar mass organic molecules [13-16]. full-size TVs. They subsequently realised that one of their electrodes had partially oxidised and was acting as a good hole-injecting contact. there are two major drawbacks for multi-user applications (e. miniature TVs. and the display image quality is highly dependent on the viewing angle of the observer. Polymer electroluminescent devices [11] offer the possibility of efficient full-colour. lungs.

(ETL and HTL refer to electron and hole transporting layers.1 Typical organic electroluminescence device configurations showing the arrangement of electrodes. carrier transport and emitting layers. but the Pioneer Corporation was the first to produce a working 64 x 256 pixel device commercially. in 1996 [18]. Many advanced display devices are expected to be marketed during the first decade of the new millennium.) The advances since this first discovery are summarised in Figure 12.2 which indicates how the drive voltage has been gradually reduced from around 100 V to a few. whilst the luminous efficiency has increased to around 100 lm/W.Polymers for Electronics Figure 12. 369 . respectively.

Handbook of Polymers in Electronics Figure 12. This problem is overcome in the research environment by carrying out device testing in an evacuated glove box with very low 370 .1a contains two organic layers between a metal cathode and an optically transparent anode. magnesium or aluminium.2 (a) Increase in luminous efficiency and (b) reduction in drive voltage since the beginning of research into organic electroluminescence The simple two-layer device shown in Figure 12. are relatively unstable in air and oxidise quite rapidly leading to short device lifetimes. and to a lesser extent aluminium. The cathode is normally a low work function metal such as calcium. Calcium and magnesium.

It must be noted here that the thickness of the transport and emitting layers are crucial in tuning the peak emission wavelength 371 . stable operation in commercial devices. A typical microcavity structure comprising a dielectric mirror at one end of the usual device configuration is depicted in Figure 12. Excited state organic molecules are formed as a result of the recombination of electron-hole pairs. More success. visible light is emitted as these excited species decay to their ground state.5. there are many examples of little or no electroluminescence being produced.3. which in turn is governed by the respective electron and hole mobilities of the electron-transport and hole-transport layers. It is tempting to believe that organic molecules exhibiting high photoluminescent efficiencies in solution (the often preferred screening medium) will therefore be useful candidates for electroluminescent devices. The almost universal anode material is ITO owing to its optical transparency and high conductivity.4 and demonstrates that polymers are available for red. A selected range of emitter materials as a function of the peak emission wavelength is shown in Figure 12. efficient encapsulation of devices will be extremely important for obtaining long-life. Several approaches to sharpening the emission spectrum of electroluminescent light output have been made.Polymers for Electronics levels of water vapour and oxygen (typically sub-ppm). The luminance output of the device is seen to be proportional to the current (density) through the device and the electroluminescence spectrum indicates that the emitted radiation is green in colour and is relatively broadband. Ideally for display applications. This is due to concentration quenching in the solid state through the formation of exciplexes and/or quenching due to interactions with oxygen or the electrode materials [19]. The current-voltage characteristic is similar to that of a traditional diode except that the turn-on voltage is much higher. Furthermore it can be easily patterned using standard photolithography and a hydrochloric acid etchant. green and blue light outputs. A typical set of device characteristics for a device containing an emitting polymer material is shown in Figure 12. has been achieved using microcavities in which both spectral sharpening and luminance enhancement can be achieved simultaneously [22]. high colour purity is desirable. One disappointing feature of most electroluminescent polymers is that the emission spectrum tends to be relatively broad (full wave half maximum (FWHM) ~100-150 nm). however. Although this is sometimes true. The wavelength of the emitted light depends on the region in which recombination takes place. Also shown are some common low molar mass materials that have been developed in parallel with their polymeric counterparts. The application of a voltage across the device results in the injection of electrons and holes (at the electrodes) which then move towards the centre of the device. These include the use of rare earth containing materials in order to utilise the atomic levels in the metal ions themselves as the electronic transition sites [20-21]. Clearly.

Handbook of Polymers in Electronics Figure 12. The electroluminescence is very similar to the PL.3 Device characteristics for a polymer light-emitting device showing (a) the current-voltage characteristic (open circles) and the luminance-voltage characteristic (filled squares) and (b) the absorbance (Abs) and photoluminescence (PL) spectra. 372 .

Spectral bandwidths have been reduced typically to 25 nm using this approach. One present difficulty is the angular dependence of the emission wavelength. The future for electroluminescent devices is certainly bright. the apparent colour of the emitted light changes slightly depending on the viewing angle as a result of the modified pathlength of the cavity. 373 .Polymers for Electronics Figure 12. One possible way of overcoming this problem is to move from a planar to a radial geometry in which each layer of the device is deposited onto a substrate containing an array of hemispherical lens-type features.4 A selected range of organic emitter materials as a function of the peak emission wavelength and intensity.

5 (a) Typical microcavity-based device structure for colour purity enhancement and (b) the resulting narrow spectral output 374 .Handbook of Polymers in Electronics (a) (b) Figure 12.

involve a 2pz orbital from each carbon atom as well as two overlapping sp2 orbitals. one from each carbon atom. for example. They are very different to traditional inorganic semiconductors.3 Conduction in Polymers Conjugated polymers have attracted great interest for a number of devices including light-emitting diodes. This equation is shown for a single carrier but in the general case where electrons and holes are involved in the conduction process. The common property linking all these applications is that the polymer must be able to support the transport of electrical charge and accept or relinquish this charge at its interface with other media. photovoltaic cells. J. μn(E) is the carrier mobility.Polymers for Electronics 12. the σ bond and the π bond together are termed the ‘double bond’. is independent of position: σ = J/E = q n μn (12. The overlapping 2pz orbitals are referred to as a π bond. field-effect transistors and photocopiers [23]. For a small organic molecule. an alternating sequence of carboncarbon single and double bonds exists. These electrons are delocalised resulting in giant extended ‘orbitals’ referred to as ‘energy bands’ that are responsible for giving charge carriers their freedom to move easily through the solid under the influence of an electric field. Carboncarbon double bonds. the electrons do not have it so easy. Equation 12. the main difference being their much lower carrier mobility (typically 10-5-10-6 cm2 V-1 s-1 compared to 103-104 cm2 V-1 s-1 for GaAs).1 shows that the current density is spatially dependent but the steady-state bulk conductivity. σ. In a conjugated molecule. on the other hand. terms can be added such that both carriers are represented. is given by: J = q {n(x)μn(E) E(x) + Dn δn(x)/δx} (12. Electrons in π bonds are much more delocalised and can roam over an extended region far beyond the vicinity of the σ bond. The electrons in these bonds are strongly localised between the two atom centres and cannot effectively participate in any conduction process. The majority of conjugated molecular materials have energy gaps in the range 1. Carboncarbon single bonds (σ bonds) form as a result of the overlap of two sp3 orbitals.0 eV and are thus viewed as wide band gap semiconductors. n(x) is the density of the carrier. the atoms are held together by covalent bonds formed by the overlapping electron sp3-hybridised orbitals.1) where q is the electronic unit charge of the carriers involved in conduction. this leads effectively to another giant (although 375 . The density of this current.5-3.2) The density of the charge carriers and their mobilities therefore determine the conductivity of a material. E(x) is the electric field and Dn is the carrier diffusion coefficient. In silicon.

6 The effect of conjugation length in polymers on the optical exciton gap 376 . the main bottleneck to the process arises from the large energy barrier for intermolecular charge transport.K/n (12. As will be mentioned later. This explains why small organic molecules are usually colourless (appearing as white crystals due to scattering) whereas longer conjugated molecules are coloured.Handbook of Polymers in Electronics not as giant as in the case of silicon) orbital stretching along the length of the conjugated region of the molecule. hence carrots are orange and grass is green due to their principal component molecules being β -carotene and chlorophyll. both molecules having regions of extended conjugation [24]. however. that very long conjugated chains twist. bend and distort quite easily.6. Egopt (infinity) is the energy gap for an infinitely long conjugated chain and K is a constant. This region is effectively a ‘cavity’ along which π electrons can move relatively easily and contribute to conduction.3) where Egopt (n) is the band gap (optical exciton or carrier energy gap) for a conjugated chain of n repeat units. The energy bandgap reduces as the length of conjugation increases as seen in Figure 12. the conductivity of a conjugated material is not merely governed by the length of the molecule. indeed. this disrupts the π-electron system so the molecule is said to possess an effective conjugation length that is dependent on the particular polymer chain environment. As the conjugation length increases. Figure 12. It should be noted. however. the energy difference between the HOMO and the LUMO decreases according to: Egopt (n) ~ Egopt (infinity) .

The interested reader should refer to the excellent review by Campbell [25].7 Polaron and bipolaron formation as a result of doping 377 . and alignment of the polymer chains (by stretching or poling for example) augments the interchain transport which is usually the limiting step of the conduction process. Figure 12.7 for PPP. These polarons or bipolarons can move along the polymer chain relatively easily and can hop from one polymer chain to another as a result of redox (polaron-transfer) reactions between neighbouring chains. If an electron accepting dopant is used. The bulk electrical conductivity is primarily dependent on the product of the number and mobility of the charge carriers. then the p-type doping results in oxidation of the polymer and the formation of a positive polaron. This process is shown in Figure 12. Many models have been developed to explain the detailed conductivity mechanisms for molecular materials but their description is beyond the scope of this chapter.Polymers for Electronics Electrons and holes on conjugated polymer chains transfer from chain to chain (molecule to molecule) in response to an applied field at a rate that determines the carrier mobility and hence the conductivity of the material. long (but not too long) conjugation regions enhance the intrachain transport. Doping increases the carrier density. also known as a radical cation. High conductivities are usually achieved by doping the polymer in order to add carriers that will subsequently be able to move through the polymer material under the influence of an electric field. Further doping results in a positive bipolar or radical dication.

Handbook of Polymers in Electronics Figure 12. 378 . Most conducting polymers have conductivities in the range 0.8 Well-known conducting polymers Even when doped.1-1 S cm-1 when fully doped [27]. The research field is advancing rapidly and this selection represents only the best-known families of polymers rather than the most conducting individual examples. A selected range of well-known conducting polymers is shown in Figure 12. PPV is commonly labelled as a conducting polymer but when undoped typically has a conductivity of around 10-14 S cm-1 and is insulating.8. An exception is polyacetylene whose conductivity has been measured to be as high as ~105 S cm-1 [26]. most ‘conducting’ polymers do not show metallic-level conductivity.

1-0. Consideration of the gradual reduction in transistor dimensions since the 1960s suggests that molecular scale transistors may be achievable shortly. thin sheets of a highly conducting polymer exhibiting conductivity comparable to that of copper. the more probable event will be the invention of completely novel electronic devices that utilise complex biological molecules as their active ingredients. In the humble opinion of this author. Moreover. Organic field electron transistors (FETs) have been developed in research groups already with mobilities around 0. Furthermore. There are many applications for such a material. however. These are varied and fall into two main categories: low-technology and futuristic high-technology opportunities. the question of making contacts at this scale has received little attention. An excellent example of this is the piezoelectric and pyroelectric coefficients of the well-known polymer. Computing based on DNA [34] is a growing discipline far removed from present-day electronic circuit approaches. the switch to organic-based electronic diodes and transistors is unlikely.and y-dimensions to similar values to the z-dimension (~2-10 nm) in order to achieve a truly molecular scale device. heavy metal boxes) and electronic circuit interconnecting tracking (to replace the miles of copper or gold currently used). 12. Speculate further about circuits in which each silicon transistor is replaced by a polymer version. the most obvious ones being coatings for electromagnetic shielding (instead of using expensive. many of the physical properties of polymers are inextricably linked to their structural and orientational order. Imagine being able to produce large.18 μm and photolithography occurs using deep ultraviolet radiation of around 190 nm. it is misleading to describe advances in the properties of polymers without also describing how such polymers are processed into thin films or crystals. again this is not farfetched. The fascination with organic electronic devices stems from the lure of miniaturisation. Their performance is poor compared to silicon transistors but it must be noted that it took just 40 years to progress from the discrete silicon transistor to a global microelectronics revolution in which the transistor gate geometry is currently 0. Metzger’s and Ashwell’s research in this area has shown that charge-transfer TTF:TCNQ-type (tetrathiafulvalene:tetracyanoquinodimethane) molecules indeed show directional conduction [32-33].5 Polymer Deposition Technologies As mentioned earlier.4 Molecular Electronics It is important to understand the driving forces behind the elucidation and development of the optical and electrical properties of polymeric materials.5 cm2 V-1 s-1 [28-30]. Little progress has been made in shrinking the x. Researchers have minimised the z-dimension (thickness) for devices such as unimolecular rectifiers [31]. polyvinylidene difluoride (PVdF) 379 .Polymers for Electronics 12.

The uniformity of the layer depends on a number of factors including the initial acceleration of the substrate and the rate of solvent evaporation.9. both of which can be easily controlled.9 The polymer spin-coating process The polymer solution flows radially outwards to form a thin solution layer that subsequently ‘sets’ as the solvent evaporates. A relatively viscous polymer solution is placed onto the substrate to be coated which is then rotated at a fixed angular speed in the range 500-4000 rpm. When this polymer is processed into thin sheets. This results from the advanced planar microelectronics and integrated optics technologies that have grown up over the last 30 years. these coefficients are close to zero. yet after stretch aligning (which causes the ordered alignment of the long polymer chains) the coefficients rise to the highest known values for organic materials. 380 . Spin coating is used most often for depositing layers of photoresist as part of the patterning process in integrated circuit fabrication. The film thickness. the most well-known and well-used method being polymer spin coating. technique is illustrated in Figure 12.Handbook of Polymers in Electronics [35]. d.4) More involved models to relate the thickness to the spinning conditions have been developed [36]. This simple. Figure 12. Generally. η. Whilst single crystals of polymers can sometimes be grown. rotation speed ω. A number of techniques exist for the deposition of polymers in thin film form. the polymer molecules within spin-coated films are relatively disordered and order has to be induced after deposition via stretch aligning or more commonly via electrical poling at elevated temperature [37]. the most common geometrical configuration of a polymer in an electronic device is a thin planar film. rendering PVdF extremely useful for pressure and heat sensing applications. solution density ρ and spinning time t and is given by: d = {η /4π ρ ω2 t}1/2 (12. depends on the solution viscosity. yet effective.

can be measured easily using a sensor that probes the water surface. There is today a huge variety in the shapes and types of molecules that can be deposited as LB films. Typically its molecular surface density in the compressed state is ~5 x 1014 cm-2 and its thickness is ~2. Each provides a means of confining the floating monolayer within an accurately controlled surface area that can be varied from a maximum value (at which the spreading process is usually performed) to a minimum value corresponding to maximum compression. two-dimensional sheet of octadecanoic acid. however. even at this point in the procedure. albeit an inhomogeneous one. After spreading and evaporation of the solvent. leaving behind the randomly distributed octadecanoic acid solute molecules. a floating Langmuir film must first be created at an air-water interface. minute droplets (each containing ~2μl) of which are then dropped carefully on the water surface.5 nm. the area available to the monolayer can be continually reduced in order to gradually compress the molecules. Usually. In practice. Octadecanoic acid (Figure 12. the polar headgroup is effectively dissolved in water. The presence of a full or partial layer of molecules at a pure water surface dramatically modifies the surface tension. which illustrates the LB process nicely. many of them being polymers [40]. thus compressing the initially expanded monolayer to form eventually a closed-packed. The solution spreads over the available water surface rapidly. the solvent evaporating fully over a period of a few minutes. A highly wettable plate (known as a Wilhelmy plate) is suspended from the microbalance using a fine. Indeed. it comprises two-dimensional solid sheets of well-packed organic molecules deposited in a predetermined. A surface pressure- 381 . The polar carboxylic group is attracted to other polar substances such as water. light and inextensible thread. Π. An LB film is an ultrathin organic assembly formed by the sequential transfer of floating Langmuir layers from a water surface onto a solid substrate.Polymers for Electronics A favoured technique by those who require highly ordered or partially ordered polymer films is LB deposition [38]. In its conventional form. The carboxyl functionality is so strong that many alkanoic acids will spontaneously spread from a bulk crystallite placed in contact with a water surface. the material is dissolved in a solvent such as chloroform. known as surface pressure. Uniformity in the surface density and thickness of the monolayer is improved by now reducing the water surface area available to the floating solute molecules. whereas the long alkyl chain is hydrophobic and is repelled by water. Langmuir and Blodgett were generally rod-shaped amphiphilic molecules such as octadecanoic acid [39]. A change in the surface tension. This amphiphilicity is responsible for giving octadecanoic acid its unique orientational properties. The first materials investigated by Pockels. an apparatus known as a Langmuir trough is used to perform the compression.10a) is an amphiphilic molecule. the most well-known being the NIMA [41] version. a monolayer film exists. yet the alkyl chain protrudes from the water surface in a near normal direction. There are many different commercial designs of Langmuir troughs available. Before the LB film can be fabricated. controllable sequence.

Handbook of Polymers in Electronics (a) (b) (c) Figure 12. a typical amphiphilic molecule.10 (a) Octadecanoic acid. (b) a schematic surface pressure-area isotherm for octadecanoic acid and (c) the orientation of octadecanoic acid molecules in a monolayer 382 .

providing insight into the relationships between the detailed molecular structure and the molecular orientation at the air-water interface. which drive the confinement belts responsible for confining the monolayer. Inspection of this isotherm is useful to obtain an insight into the orientation of the molecules within the monolayer. A schematic diagram of a typical Langmuir trough is shown in Figure 12. 383 . The transfer of floating Langmuir films onto solid supports is in principle a straightforward process involving the successive insertion and withdrawal of a substrate through the monolayer film at the air-water interface. which describes the change in surface tension of the water surface as the floating monolayer is compressed.2 nm2. At large area in its expanded state. Such measurements have been made for a huge number of different materials. The transfer of the first monolayer occurs due to the strong interaction between the carboxylic acid groups of the alkanoic acid molecules and polar sites (usually taking the form of free hydroxyl groups) on the hydrophilic substrate surface. This value corresponds closely to the cross-sectional area of the carboxyl end of the molecule as shown in Figure 12. This ensures that the small decrease in the surface pressure that results when part of the monolayer is transferred onto a solid substrate stimulates further compression of the monolayer in order to restore the original preset deposition surface pressure.Polymers for Electronics area isotherm. is shown for an alkanoic acid in Figure 12. monolayer fluidity. substrate cleanliness and surface treatment. the surface pressure is close to zero indicating that only weak interactions are occurring between molecules.12. pH and ion content of the sub-phase and temperature.10b. This ensures that the molecular surface density within the transferred monolayer remains constant. The LS region represents a state of high incompressibility such as found in a traditional three-dimensional solid. the deposition rate (rate of withdrawal and/or rate of insertion). This implies that the floating film is indeed monomolecular in dimension.10c. The sequential transfer process for a hydrophilic substrate withdrawn and inserted through an alkanoic acid monolayer is shown in Figure 12. The most fundamental requirement is that of a highly stable feedback mechanism between the surface pressure monitors and the motors. the surface pressure begins to rise – this region is referred to as the liquid-condensed region (L2) and corresponds to phases in which the molecules are tilted relative to the plane of the water surface. Its success depends on the optimisation of a number of controlling variables such as the deposition surface pressure. Indeed the LS region used to be referred to as the ‘solid’ region of the isotherm [42].11. The substrate insertion and withdrawal is normally achieved using a motor-driven micrometer screw to which is attached the clamp for the substrate. As the confinement area of the monolayer is decreased further. Further compression results in the formation of the superliquid (LS) phase in which the alkyl chains protrude almost orthogonally from the plane of the water surface. The area occupied on the water surface by a single alkanoic acid molecule within the monolayer is about 0.

11 A typical Langmuir trough for the fabrication of LB films showing the surface pressure monitor (P). the substrate (S) attached to the deposition mechanism (D) via the clamp (C). 384 . Figure 12. the moveable constant perimeter barriers (MB). Inset: Y. X and Z-type architectures. the wettable plate (W).12 The sequential monolayer transfer process for the formation of LB films showing the formation of Y-type assemblies. the barrier drive motors (BD) and the water bath (B).Handbook of Polymers in Electronics Figure 12.

Such an apparatus is depicted in Figure 12. and between hydrophilic carboxyl groups that can form hydrogen bonds across the interface between layers and in-plane sideways dimers that serve to strengthen the layers laterally. then an overall electric polarisation results which is an additive function of μ1 + μ2. Unfortunately. several researchers have found that Z. dipoles μ1 and μ2 would not cancel completely and indeed. can only be deposited during each upstroke (Z-type deposition) and others only during each insertion (X-type). polar groups. so that the resulting architecture is pseudo Y-type. Most rodshaped amphiphilic molecules follow this mode of deposition as do most pendant-chain polymers. This process can be repeated over many cycles and is referred to as Y-type deposition. The type of deposition followed by a particular material affects the properties of the resulting LB films due to symmetry restrictions for second-order physical effects such as piezoelectricity or optical second-harmonic generation. The resultant stability of this system is clearly a trade-off between the structural stability arising from the pseudo Y-type architecture and the energetic stability that is expected to gradually reduce as the number of transferred layers increases owing to the large build-up in electric polarisation [47].and X-mode multilayers are often temporally unstable. There is a strong hydrophobic interaction between the alkyl chains within the first monolayer (the new substrate surface for the second layer) and those protruding from the water surface in the floating monolayer. such as many phthalocyanines [45]. Therefore. A and B.and Xtype modes. The bilayer unit (equivalent to the unit cell in a crystal) is symmetric for Y-type deposition but non centric for Z. although the zwitterionic dyes of Ashwell prove to be one of the exceptions [46]. as do the hydrophilic. alkyl chains from adjacent monolayers interact hydrophobically. Thus.13 and this shows how two independent water surfaces are used to carry two different monolayers.12. if the molecules have been designed such that μ1 and μ2 act in opposite directions with respect to their alkyl chains. However. One solution to achieving non centrosymmetry within stable multilayer films is to use the alternate layer LB deposition technique. the alkyl chain regions act as screening layers meaning that multilayer films 385 . The deposition sequence is ABABABA…. like polysiloxanes [43-44]. A second layer is thus adsorbed and the surface of the coated substrate becomes hydrophilic again and is thus ready to accept the third monolayer upon its next withdrawal through the Langmuir film. Certain materials.Polymers for Electronics Reinsertion of the monolayer-coated substrate results in the transfer of the second monolayer. This employs a special kind of Langmuir trough known as an alternate layer trough that is effectively two single-compartment troughs hybridised into one unit. Such assemblies are generally very stable over time owing to the strong stabilising interactions between hydrophobic chains from adjacent monolayers. the difference here is that the molecules within layers A and B are inherently different. as indicated in Figure 12. This deposition mode results essentially (except for the first monolayer) in a non centrosymmetric structure.

Handbook of Polymers in Electronics

Figure 12.13 Alternate layer Langmuir trough showing the substrate attached to the rotating drum (R). All other symbols have the same meaning as in Figure 12.11.

containing up to ~200 layers can often be deposited without structural degradation. Alternate layer LB films have been adopted most commonly for studies concerning non linear physical phenomena such as piezoelectricity, pyroelectricity and optical secondharmonic generation.


Polymers for Electronics Although the LB approach is applicable to an ever-increasing range of materials, water-soluble compounds are excluded. In a much lower technology, yet elegant, deposition process, water-soluble polymers can be deposited layer by layer to form similar molecular assemblies to LB films [48]. This method, generally known as the polyelectrolyte layer-by-layer self-assembly process, makes use of the ionic attraction between opposite charges on anionic and cationic electrolytes. A solid substrate is positively charged by chemical cleaning methods and is placed in a solution of an anionic polyelectrolyte, such as poly (sodium 4-styrenesulfonate) [49]. The deposition process is depicted in Figure 12.14. During a period of around 10 minutes, a monolayer of the polymer is adsorbed onto the substrate surface via the electrostatic attraction. The process is self-regulating since a second monolayer of the anion cannot be adsorbed due to electrostatic repulsion since there are many unpaired anionic charges on the polymer which remain electrostatically unsatisfied. Therefore, after monolayer adsorption, the coated substrate is washed thoroughly in water and then placed in a solution of a cationic polyelectrolyte, such as poly(alylamine hydrochloride [50]. Again ionic attractions result in the adsorption of a cationic monolayer. This procedure can be repeated many times to build up alternate layer polymer films. The advantages of this method over LB deposition are that it is very easy to perform and applicable to water-soluble polymers; the drawback, however, is that the rate of deposition is limited to around 5 monolayers per hour compared to conventional LB deposition rates of 20 monolayers per hour. Recent developments in LB technology have led to much higher rates approaching 30 monolayers per minute [51].

Figure 12.14 The layer-by-layer polyelectrolyte self-assembly process for charged polymers


Handbook of Polymers in Electronics

12.6 Summary
Much progress has been made in the development of polymers for electronics applications over the last 20 years. The next few years will see the impact of flat-screen displays based on organic materials and the continued development of biological electronics for biosensing and biocomputing applications. The amazing developments in the microelectronics sector over the last few decades has been driven by the insatiable demand for technology to improve mankind’s quality of life and to accelerate further progress. A similar development in the fabrication of organic circuits may or may not occur depending on the perceived advantages of moving away from silicon. Certainly if it were to happen, it would take much less than 40 years. Undoubtedly, this research area is set to attract increasing attention and to produce devices that are as of yet totally inconceivable.

The author would like to thank Al Campbell, Dave Lidzey, Rob Fletcher, Colin Dooling, Pierre Oliviere and O. Worsfold for helpful discussions during the preparation of this chapter.

1. 2. G.G. Roberts, Langmuir-Blodgett Films, Plenum Press, New York, NY, USA, 1990. M.C. Petty, M.R. Bryce and D. Bloor, Introduction to Molecular Electronics, Edward Arnold, London, UK, 1995. William Jones, Organic Molecular Solids: Properties and Applications, CRC Press, Boca Raton, FL, USA, 1997. T.H. Richardson, Functional Organic and Polymeric Materials: Molecular Functionality – Macroscopic Reality, John Wiley & Sons, Chichester, UK, 2000. J.H. Burroughes, D.D.C. Bradley, A.R. Brown, R.N. Marks, K. Mackay, R.H. Friend, P.L. Burns and A.B. Holmes, Nature, 1990, 347, 6293, 539. M. Pope, H.P. Kallmann and P. Magnante, Journal of Chemical Physics, 1963, 38, 2042. T. Iwayanagi, T. Ueno, S. Nonogaki, H. Ito and C.G. Wilson in Electronic and Photonic Applications of Polymers, Eds., M.J. Bowden and S.R. Turner, ACS, Washington, DC, USA, 1988, 109.







Polymers for Electronics 8. M. McCallum, K.R. Dean and J.D.Byers, Microelectronic Engineering, 1999, 46, 1-4, 335. M.W. Poulter, National Semiconductor Inc., Santa Clara, California, USA, 2000 (Private Communication).


10. D.A. Dunmur and L.D. Farrand in Functional Organic and Polymeric Materials: Molecular Functionality – Macroscopic Reality, Ed., T.H. Richardson, John Wiley & Sons, Chichester, UK, 2000, 31. 11. D.D.C. Bradley, Current Opinion in Solid State Materials Science, 1996, 1, 789. 12. C.W. Tang and S.A. VanSlyke, Applied Physics Letters, 1987, 51, 913. 13. P.S. Vincett, W.A. Barlow, R.H. Hann and G.G. Roberts, Thin Solid Films, 1982, 94, 171. 14. C. Adachi, S. Tokito, T. Tsutsui and S. Saito, Japanese Journal of Applied Physics, 1988, 27, L269. 15. R.H. Partridge, Polymer, 1983, 24, 733. 16. C.W. Tang, S.A. VanSlyke and C.H. Chen, Journal of Applied Physics, 1989, 65, 3610. 17. A.J. Hudson and M.S. Weaver in Functional Organic and Polymeric Materials: Molecular Functionality – Macroscopic Reality, Ed., T.H. Richardson, John Wiley & Sons, Chichester, UK, 2000, 365. 18. H. Inada, Y. Yonemoto, T. Wakimoto, K. Imai and Y. Shirota, Molecular Crystals and Liquid Crystals Science and Technology Section A, 1996, 280, 331-336. 19. C. Adachi, T. Tsutsui and S. Saito, Applied Physics Letters, 1989, 56, 799. 20. J. Kido, K. Nagai, Y. Okamoto and T. Skotheim, Chemical Letters, 1991, 1267. 21. M. Weaver, S. Martin, D.D.C. Bradley, M. Pavier, T. Searle and T.H. Richardson, Synthetic Metals, 1995, 76, 1-3, 91. 22. D.G. Lidzey, M.S. Weaver, T.A. Fisher, M.A. Pate, D.M. Whittaker, M.S. Skolnick and D.D.C. Bradley, Synthetic Metals, 1996, 76, 1-3, 129. 23. M. Stolka in Special Polymers for Electronics and Optoelectronics, Eds., J.A. Chilton and M.T. Goosey, Chapman and Hall, London, UK, 1995, 284.


Handbook of Polymers in Electronics 24. L.R. Milgrom, The Colours of Life: An Introduction to the Chemistry of Porphyrins and Related Compounds, Oxford University Press, Oxford, UK, 1997. 25. A.J. Campbell in Functional Organic and Polymeric Materials: Molecular Functionality – Macroscopic Reality, Ed., T.H. Richardson, John Wiley & Sons, Chichester, UK, 2000, 201. 26. H. Naarmann and N. Theophilou, Synthetic Metals, 1987, 22, 1. 27. S. Roth, One-Dimensional Metals: Physics and Materials Science, VCH, Weinheim, Germany, 1995. 28. W.P. Hu, Y.Q. Liu, Y. Xu, S.G. Liu, S.Q. Zhou and D.B. Zhu, Molecular Crystals and Liquid Crystals Science and Technology Section A: Liquid Crystals and Molecular Crystals, 1999, 337, 511. 29. Y.Y. Lin, D.J. Gundlach, S.F. Nelson and T.N. Jackson, IEEE Electronic Device Letters, 1997, 18, 12, 606. 30. J.G. Laquindanum, H.E. Katz, A. Dodabalapur and A.J. Lovinger, Journal of the American Chemical Society, 1996, 118, 45, 11331. 31. A. Aviram and M.A. Ratner, Chemical Physics Letters, 1974, 29, 277. 32. R.M. Metzger, B. Chen, U. Hopfer, M.V. Lakshmikantham, D. Vuillaume, T. Kawai, X. Wu, H. Tachibana, T.V. Hughes, H. Sakurai, J.W. Baldwin, C. Hosch, M.P. Cava, L. Brehmer and G.J. Ashwell, Journal of the American Chemical Society, 1997, 119, 10455. 33. R.M. Metzger, Advanced Materials for Optics and Electronics, 1998, 8, 229. 34. M. Ogihara and A. Ray, Nature, 2000, 403, 143. 35. T. Furukawa, M. Date and E. Fukada, Journal of Applied Physics, 1980, 51, 1135. 36. W.W. Flack, D.S. Soong, A.T. Bell and D.W. Hess, Journal of Applied Physics, 1984, 56, 1199. 37. M. Petty, J. Tsibouklis, M.C. Petty and W.J. Feast, Ferroelectrics, 1993, 150, 267. 38. T.H. Richardson in Functional Organic and Polymeric Materials: Molecular Functionality – Macroscopic Reality, Ed., T.H. Richardson, John Wiley & Sons, Chichester, UK, 2000, 181.


Polymers for Electronics 39. I.R. Peterson, Thin Solid Films, 1984, 116, 357. 40. R.A. Hann in Langmuir-Blodgett Films, Ed., G.G. Roberts, Plenum Press, New York, NY, USA, 1990, 68. 41. Nima Technology Limited, http://www.nima.co.uk 42. I.R. Peterson in Functional Organic and Polymeric Materials: Molecular Functionality – Macroscopic Reality, Ed., T.H. Richardson, John Wiley & Sons, Chichester, UK, 2000, 109. 43. T.H. Richardson, W.H.A. Majid, R.Capan, D. Lacey and S. Holder, Supramolecular Science, 1994, 1, 1, 1. 44. D. Lacey, S. Holder, W.H.A. Majid, R. Capan and T.H. Richardson, Materials Science & Engineering, 1995, C99. 45. C.C. Leznoff and A.B.P. Lever, Phthalocyanines: Volume 1 – Properties and Applications, VCH, New York, NY, USA, 1989. 46. G.J. Ashwell, P.D. Jackson and W.A. Crossland, Nature, 1994, 368, 438. 47. P. Christie, G.G. Roberts and M.C. Petty, Applied Physics Letters, 1986, 48, 1101. 48. G. Decher, J.D. Hong and J. Schmitt, Thin Solid Films, 1992, 210/211, 831. 49. G. Decher, Y. Lvov and J. Schmitt, Thin Solid Films, 1994, 244, 772. 50. W.B. Stockton and M.F. Rubner, Macromolecules, 1997, 30, 2717. 51. T.H. Richardson, C.M. Dooling, O. Worsfold, L.T. Jones, K. Kato, K. Shinbo, F. Kaneko, R. Tregonning, M.O. Vysotsky and C.A. Hunter, Colloid and Surfaces A, 2002, 198-200, 843.


Handbook of Polymers in Electronics



Conducting Polymers in Molecular Electronics
B. D. Malhotra, V. Saxena, A. Gambhir, R. Singhal, S. Annapoorni and A. Mukhopadhyay

13.1 Introduction
Electronic technology has developed enormously over the past decades. The trend is to make better, faster and smaller electronic devices for use in our daily living. Most of the electronic devices are fabricated directly on semiconductor silicon. Today’s advanced silicon chip can store sixteen million bits of information within an area less than 1 cm2. However, there is a practical limit to the capacity of the storage of information within the chip. It is being conjectured that as chip density increases, crosstalk between them tends to degrade their performance. If the components are pushed further, they may short-circuit. This inherent technical difficulty has led to the evolution of the field of molecular electronics. Molecular electronics (ME) is so named because it uses molecules to function as ‘switches‘ and ‘wires’. ME is a term that refers both to the use of molecular materials in electronics and to electronics at molecular level. It is as yet not very clear how molecular electronic devices will operate, but it is conjectured that active molecules are needed, either in isolation or becoming active by association with other molecules. It is thought that electronics is likely to imitate some of the basic functions of macroscopic devices such as memories, sensors and logic circuits. Organic molecules such as conducting polymers, proteins and pigments are being considered as alternatives for carrying out the same functions that are presently performed by semiconductors (e.g., silicon) and metals. Among them, conducting polymers (or conjugated polymers) have been considered as highly promising for molecular electronics [1-5]. These conducting polymers offer a unique combination of properties that make them attractive materials for use in molecular devices (Figure 13.1). The conductivity of these polymers can be tuned by chemical manipulation of the polymer backbone, by the nature of the dopant, by the degree of doping and by blending with other polymers. In addition they offer lightweight, processibility and flexibility. Because of these advantages, the use of conducting polymers in molecular electronics is rapidly evolving from physics, chemistry, biology, electronics and information technology. These molecular electronic materials differ from conventional polymers by having a delocalised electronic structure that can accommodate charge carriers such as electrons and holes. Besides this, these organic materials


Handbook of Polymers in Electronics

Figure 13.1 Applications of conducting polymers in molecular electronics

exhibit Peierl’s instabilities due to the built-in high anisotropic interactions and undergo substantial geometric modifications due to electronic excitations. This results in various charge transfer processes and a substantial degree of disorder leading to various localised states in the forbidden gap due to localisation. Conducting polymers exhibit the behaviour of both metal and semiconductor. Polyacetylene, the first and simplest electrically conducting polymer, doped with iodine (I2) has been shown to have an electrical conductivity of 1000 S cm-1 [2]. Some of the conducting polymers that have recently generated much interest are shown in Figure 13.2. It can be seen that conducting polymers behave as anisotropic semiconductors with band gaps in the range 1.4-3.2 eV. It has been suggested that electrical conduction in the conjugated polymers occurs via non linear (or topological) defects (solitons or polarons/biploarons) generated either during polymerisation or as a consequence of doping [6, 7]. Solitons can be produced as a result of an interruption in the structure of a degenerate conducting polymer such as trans-polyacetylene (Figure 13.3a). In other conducting polymers such as polypyrroles, polyanilines and polythiophenes, etc., the charge


Conducting Polymers in Molecular Electronics

Figure 13.2 Structures and band gaps of some important conducting polymers


Handbook of Polymers in Electronics

Figure 13.3 Energy band diagram of (a) soliton (b) polaron and (c) bipolaron

carrier is a polaron [8], a non linear defect that occurs as a result of localisation of charge in a polarised lattice of a conjugated polymer (Figure 13.3b). Due to increased doping, the concentration of non linear defects (solitons/polarons) increases resulting in an enhanced electrical conductivity. It has been shown that increased electrical conductivity in highly conducting polymers is spinless which results due to the formation of bipolarons (a bipolaron is a bound state of two polarons) [9, 10]. The concentration of bipolarons can be increased as a consequence of external stimuli (doping/heat/irradiation) on a conducting polymer. Solitons and polarons have recently been shown to have implications in the technical development of molecular electronic devices [11]. The development of molecular electronics is dependent upon the synthesis and tailoring of ‘active molecules’ and is a great challenge to researchers. Conducting polymers can be prepared both by chemical and electrochemical techniques. The nature of a monomer


Conducting Polymers in Molecular Electronics governs the selection of a method. For example, polyacetylene is prepared by polymerisation of acetylene using a Ziegler-Natta catalyst at low temperatures [12]. Heterocyclic polymers, such as polyaniline, polypyrrole and poly(p-phenylene), have been synthesised using the electrochemical technique [13-15]. Due to ease of handling and control of thickness, the electrochemical technique has been extensively used for technical development of molecular electronic devices. By varying the nature of the groups, specific interactions with external physical and chemical phenomena can be developed in these materials, leading to molecular devices such as transducers, memories and logic operators. Characterisation of conducting polymers is very important for investigating the electronic processes occurring in molecular electronic materials. A variety of techniques (electrochemical, optical, ESR, SEM, AFM, gel permeation chromatography (GPC)) have been widely used to delineate the physical properties of the conjugated polymers [16-20]. For example, the changes in the optical spectra accompanied with doping have been considered very significant in elucidating the mechanism of structural changes in the polymer chains. Information on morphological changes has been found very helpful towards the fabrication of lightweight batteries [21, 22]. Electrochemical characterisation provides information regarding redox behaviour, the number of electrons in the redox reaction and diffusion coefficient estimation of conducting polymers [23-25]. Thermal techniques such as DSC and TGA reveal valuable information on the thermal stability and degradation of these organic molecular electronic materials [26-28]. Time-of-flight (TOF) measurements have recently been used to estimate the magnitude of charge carrier mobility in conducting polymer systems [29]. It is emphasised that the experimental data accumulated as a result of characterisation plays a significant role in the application of a desired conducting polymer to molecular electronic applications. Conducting polymers have been shown to have a number of potential technological and commercial applications in optical, drug delivery, memory and biosensing devices [3034]. Among these, application of conducting polymers to molecular electronics has attracted the maximum attention. The major challenge confronting the materials scientists, including biochemists and physicists, is how the properties of these electronic materials differ from those of conventional semiconductors. Our group has been actively engaged in the research and development of conducting polymer-based molecular electronic devices for the past fifteen years [35-39]. It was, therefore, thought that a review based on the recent research findings will prove helpful to the researchers venturing to enter this highly fascinating field of molecular electronics.

13.2 Synthesis of Conducting Polymers
Conducting polymers have been prepared by both chemical and electrochemical techniques. Conducting polyheptadiene has been obtained by cycling 1,4-heptadiene in the gas phase


2´-bipyridyl ruthenium) complex as a photosynthesiser.8-bis(trifluoromethyl)tricyclodeca-3. the polymerisation temperature. A solid-state polymerisation method makes use of monomer crystals using heat or light. The advantage of this technique lies in the easier control of the polymerisation reaction to a desired surface. potentiostatic and potentiodynamic (or cyclic sweep). Polyacetylene can also be polymerised by the Durham route [41. Photopolymerisation utilises photons to initiate a desired polymerisation reaction in the presence of photosynthesisers. the acetylene pressure and the ageing condition. Polypyrrole has been reportedly synthesised from pyrrole using a tris (2. In the potentiostatic mode. Polythiophene has been synthesised by both electrochemical [45] and chemical techniques [46]. chloroform and n-methylpyrrolidone. Polydiacetylene and polysulfur nitride with perfect stereoregularity have been prepared using this technique. The method makes use of monomers to form cations followed by their coupling to form dications. The selection of the 398 . Wang and co-workers [48] later systematically investigated the effect of temperature on the synthesis and properties of poly(aniline-co-orthoanisidine). Synthesis of poly(arylenevinylene) involves preparation of a water-soluble dimethyl sulfonium salt as a precursor monomer. The oxidative coupling method is one of the best methods for obtaining high molecular weight poly(paraphenylene) [44]. polyaniline can be prepared using aqueous and non aqueous routes using chemical technique [43]. Electrochemical oxidative polymerisation is known to be an effective method for obtaining conducting polymers [49]. its base-catalysed polymerisation and subsequent thermal elimination to yield the conducting poly(arylenevinylene). In galvanostatic mode. It has been found that the plasmapolymerised films are usually highly crosslinked and are resistant to higher temperatures and chemicals. Besides this. a conducting polymer is generated by supplying a constant current between a working electrode and a counter electrode. There are three methods: galvanostatic. Polymerisation on the wall of a reaction flask depends on the catalyst activity and preparative conditions such as the Al/Ti ratio. in which 7.7. This technique results in very thin but uniform polymeric layers that strongly adhere to a desired substrate. Plasma polymerisation makes use of molecules occurring in various plasma environments. Films produced by this method are smooth and adherent to the anodic surfaces. the conducting polymer is grown at a predefined constant potential maintained between the counter and working electrodes.Handbook of Polymers in Electronics by selective deposition on polyethylene and Teflon. 42]. Pandey and co-workers [47] have reported the chemical synthesis of poly(anilineco-orthoanisidine) that has been found to be soluble in common organic solvents such as acetone.9-triene is used as a monomer and CuCl6:(C6H5)4Sn (1:2) and TiCl4:(C2H5)3Al (1:2) are used as catalyst. Polyacetylene has been prepared by allowing acetylene to polymerise on the wall of a reaction flask on which the catalyst solution containing Ti-[O-n-C2H9]4 and [C2H5]3Al is coated [40]. It has been revealed that this processable conducting polymer has application in molecular electronic devices. and repetition of this process produces a conducting polymer.

Langmuir-Blodgett films are formed by first depositing a small quantity of an amphiphilic material (stearic acid) dissolved in a volatile organic solvent onto the surface of purified water (sub-phase).3.4) is recorded by compressing the monolayer mechanically [54. These materials are known as amphiphiles. the compression causes the molecules to be aligned in the same way on the surface of water (Figure 13.1 Langmuir-Blodgett Films The preparation of polymeric Langmuir-Blodgett films with different characteristics is of great scientific and technological interest. 51]. 53]. On evaporation of the solvent. It can be remarked that this method produces powdery deposits that are non adherent to the electrode surface. This has been considered to be an attractive alternative if ordered structures are required.. 399 . polyaniline) by this method is obtained from polarisation studies. Apart from these. the pressure-area isotherm (Figure 13. It has been found that this method gives homogeneous conducting polymer films that strongly adhere to the electrode surface. 55]. the potential is cycled between two predefined potentials with a definite sweep rate. The flexible and smooth films can be prepared by the judicious selection of the conducting salt acting as an electrolyte. counterions [organic/inorganic] and also the substrate play a key role in the mechanical and electrical properties of conducting polymers prepared using electrochemical techniques. This results in the formation of the floating organic material into a ‘two-dimensional solid’. It can be seen that the electrochemical method is an advancement over chemical techniques because the resulting product does not need to be extracted.. In the case of the potential cycling (i.Conducting Polymers in Molecular Electronics constant potential for the synthesis of a conducting polymer (e.5). 13. It has been shown that it is possible to obtain by these techniques a system of ‘wires’ and ‘switches‘ comprising of conducting polymer monolayers [52.3 Preparation of Ultrathin Conducting Polymer Films Ultrathin films of conducting polymers have been projected to have applications in molecular electronics [50. It has been ascertained that the charge and the geometry of the anions greatly affect the properties of a given conducting polymer. 13. Materials that form monolayers on the surface of water comprise of molecules that contains both hydrophilic (water-attracting) and hydrophobic (water-repelling) chemical groups. The approach lies in fabricating devices starting from atoms and molecules. cyclic voltammetry) method. It is thought that an understanding of the physical properties of conducting polymer monolayers will prove very valuable in the evolution of the area of molecular electronics.e.g. And since the amphiphile has hydrophobic and hydrophilic ends. some general considerations such as the choice of the solvent.

this is called X-type deposition.4 Pressure-area isotherm of an Langmuir-Blodgett film of poly(3-hexylthiophene) Figure 13. If a layer is deposited on the substrate only when the solid substrate enters the sub-phase. On the other hand if a layer is deposited on the substrate when withdrawn 400 . However. if the solid substrate is hydrophobic a monolayer will be deposited as it is first lowered into the sub-phase.Handbook of Polymers in Electronics Figure 13. thus a Y-type film containing an even number of monolayers can be fabricated (Figure 13. This results in an odd number of monolayers being transferred onto the solid substrate.7). If the substrate is hydrophilic the first monolayer is transferred as the substrate is raised through the sub-phase. This deposition mode is referred to as Ytype deposition.6).5 Possible orientations of a molecule deposited by Langmuir-Blodgett technique The molecules in their closest packed arrangement (solid phase) are removed from the surface of water by suitably dipping and raising a suitable plate (substrate) through the air/water interface in three ways (Figure 13. these stack in a head-to-head and tail-to-tail configuration.

and Z-type deposition in Langmuir-Blodgett film deposition Figure 13. (b) Deposition of first monolayer on withdrawal of hydrophilic substrate. (d) Deposition of third monolayer in a head-to-head and tail-to-tail configuration 401 . Y.Conducting Polymers in Molecular Electronics X Y Z Figure 13.6 X-. (a) Compressed monolayer of molecules on water surface. (c) Deposition of second monolayer on insertion of hydrophilic substrate.7 Schematic of Y-type deposition in a Langmuir trough.

Film deposition can be characterised by knowing the deposition ratio. They showed that the chemistry initiated at the air-water interface and the properties of the resultant polymer are strongly influenced by the type of the surface-active monomer used. The results of atomic force measurements conducted on a five-layer polythiophene film revealed that the rearrangement of molecules occurs resulting in a fibrous structure. Energy transfer between excited molecular states and model membranes has been used to mimic photosynthetic systems. crosslinkage and denaturing. for X-type. The pyrrole/3ODOP film was found to be highly aniosotropic with conductivity in the plane being 107 times greater than the conductivity across the film thickness.1) where Al is the decrease in the film area of the sub-phase and As is the contact area of the substrate. τ. φ = 0. Many factors such as temperature. humidity and pH (aqueous phase) can influence measurements on interfacial films. Langmuir-Blodgett films are ideal systems for spectroscopy of complex monolayers. Langmuir-Blodgett films of a number of conducting polymers such as polypyrroles.2) where τu and τd are the deposition ratio on the upward and downward passage. Various deposition modes can be obtained using a parameter φ given by Hoing and coworkers [57]: φ = τu / τd (13. Bardosova and co-workers [59] have investigated the formation of polythiophene Langmuir-Blodgett films on silicon. and for Z-type deposition. Ultrathin films of 3-octadecylpyrrole (3ODP) and 3-octadecanoylpyrrole (3ODOP) were subsequently obtained using Langmuir-Blodgett technique. 402 . φ =1. etc. respectively. It has recently been demonstrated that the Langmuir-Blodgett technique can be utilised to process a variety of conductive polymeric systems into multilayer films. the latter being by way of charge-transfer interactions. it is called Z-type deposition. Hoing and co-workers [58] have shown that electrically conducting polypyrrole films can be formed at the airwater interface of a Langmuir-Blodgett trough using a solution containing a surface-active pyrrole monomer and a large excess of pyrrole on a sub-phase containing ferric chloride (FeCl3). as given by Langmuir and co-workers [56]: τ = Al / As (13. polyanilines and poly-(o-anisidines). For the Y-type deposition. have recently been prepared.Handbook of Polymers in Electronics from the sub-phase. The conjugated polymer backbone provides a route for the flow of electrons either along the molecule or between nearest neighbours. φ = ∞.. Langmuir-Blodgett films offer ways of studying molecular conformational changes and providing information on molecular packing.

which are required for a polymerisation. It was found that the multilayer films exhibit poor electrochromic response. real-time optical data processing systems. biosensors and chemical sensors. The ability to tailor properties of conducting polymer films has been of advantage for several applications. Matsura and co-workers [67] have fabricated monolayers of β-carotene using a Langmuir-Blodgett film technique together with the flow-orientation method. However.Conducting Polymers in Molecular Electronics Aghbor and co-workers have obtained films of deposition of preformed polyemeralidine base (PEB) by dissolving PEB in a N-methylpyrrolidone/CHCl3 mixture in an aqueous subphase containing acetic acid [60]. The best-known example is of liquid crystalline polymers that have potential applications in electro-optic applications such as calculators. The molecular order existing in Langmuir-Blodgett multilayers facilitates the formation of liquid crystalline polymer substances since some of the conditions are easily met. The molecular electronic applications of conducting polymer Langmuir-Blodgett films include microactuators. wristwatches. ultrathin films of poly(o-anisidine) and poly(ethoxyaniline) have been fabricated for application in nanotechnology [64-66]. well-ordered both in the stacking direction and the in-plane direction. • • Conducting polymer Langmuir-Blodgett films find applications in insulation. waveguide switches. resulting in its reduced electroactivity. Recently. adhesion and encapsulation. 62] subsequently showed that it is possible to obtain quasi-ordered Langmuir-Blodgett films of emeraldine base without incorporating fatty acid tails in the molecule. These results have implications in the fabrication of molecular devices. Dabke and co-workers [63] studied the electrochemistry of polyaniline Langmuir-Blodgett films using cyclic voltammetry coupled with a quartz microbalance. Schottky devices. It is 403 . and The chain period of the polymer must coincide with a transitional period of the monomer crystal lattice. flat panel televisions. The overlapping volumes of monomer units in the polymer chain should not much differ from that of the monomer molecule. It was found that the films are. It may be emphasised that the industrial use of each of these applications is closely linked with manipulating the architecture of a conducting polymer via ‘molecular engineering’. etc. high-density information storage. however. message boards. highdefinition television. UV-visible and FTIR techniques to elucidate the film-structure of β-carotene indicating that β-carotene orients perpendicular to the air-water interface. These conditions are: • The volume contraction during the chain formation should not be in the direction of chain growth. the results of cyclic voltammetery and chronopotentiometry indicate that irregularities begin to form in the film and the ordered nature of the films is lost. Ram and co-workers [61. They have utilised XRD.

2 Self-Assembly Monolayers One of the methods of formation of organised monolayer assemblies (OMAs) on the desired solid surface has been described in the preceding section. 13. scanning tunneling microscopy (STM) and AFM techniques [79-82].Handbook of Polymers in Electronics appropriate to mention here that the Langmuir-Blodgett technique provides an opportunity to control the thickness and supermolecular organisation of electroactive polymers at the molecular level for application to the potential field of molecular electronics. The morphology of conducting polymer films has been investigated using optical microscopy. 13. The molecular weight of a conducting polymer has been estimated by GPC. Thermal techniques such as DSC/DTA have been utilised to check the stability of conducting polymers in air.4 Characterisation of Conducting Polymers Characterisation of a conducting polymer is important before it can be used for any technological application. Monolayers of polythiophene and substituted polythiophene have been formed on gold substrates by a dipping method [69]. SEM/TEM. Different conjugated and non conjugated polymers in the form of bilayers have been used to make heterostructures.3. It has been shown that the origin of magnetic properties in a conjugated polymer lies in its π-electron system. These self-assembled monolayers have potential for technological and scientific applications ranging from microelectronics to biological sensors [68]. Dielectric relaxation and low frequency conductivity measurements in the frequency range from 100 to 107 Hz have proven valuable in giving information on the mechanism of conductivity that cannot be obtained with dc conductivity data alone [78]. this technique has been utilised for preparing multilayers of polyaniline and polypyrrole samples with uniform ordering [68]. Another process is the method of self-assembly wherein the molecules are transferred to the surface of a solid from the liquid phase by a dipping process. Here the molecules are held by the electrostatic attraction of the alternatively charged polymers. ESR measurements have been found to reveal information on the phenomenon of doping in electrically conducting polymeric systems. Another approach to fabricating self-assembled monolayers is by depositing alternating layers of p. Converting the polymer into a polycation or a polyanion by using the appropriate acidic solution produces the charges. For example. Multilayered thin films with precisely controlled thickness and layer sequences can also be obtained by this technique [70-76].and n-type polymers on a suitable substrate. Studies conducted on the morphology 404 . Physical and chemical properties of conducting polymers have been investigated by a number of experimental techniques. which has also been considered as the reason for the observed chemical properties [77].

F–. it has been shown that the fibrillar structure of polyacetylene is often advantageous since it can store up to about 7% of electrical charge [85]. ClO4 .Conducting Polymers in Molecular Electronics – of conducting polypyrrole films containing different anions such as NO3–. AFM and STM methods [86] have recently provided valuable information on the presence of microdomains in poly(3-hexylthiophene)/stearic acid films (Figures 13. BF4– and CH3C6H4SO3–. respectively.9).9 Scanning electron micrograph of conducting poly(3-hexylthiophene) 405 .8 Atomic force micrograph of conducting poly(3-hexylthiophene) Figure 13. have revealed that the topology of the growing conducting polypyrrole surface is influenced by the nature of the electrolyte [83-84]. For instance.8 and 13. Figure 13.

5 Molecular Devices Based on Conducting Polymers 13. It has been revealed that carrier concentration. The characteristics of conducting polymer/inorganic semiconductor interfaces have been considered as very important since it has been indicated that restrictions on Schottky barrier devices can be overcome by using conducting polymer contact layers. 13. polypyrrole and polyaniline have recently been used for the fabrication of Schottky barrier diodes. Photoelectron spectroscopy methods have been used as probes to investigate electronic and chemical structures of conducting polymers such as polypyrroles and polythiophenes.10. The application of spectroscopic techniques in the IR and UVvisible regions to conducting polymers has brought interesting information on the configurational changes arising as a consequence of doping.Handbook of Polymers in Electronics Spectroscopic methods have been used to yield information on the charge transport behaviour in conjugated polymers. plays an important role in controlling the junction 406 . respectively. A schematic diagram for a Schottky device is shown in Figure 13. the ability to manipulate the interface characteristics by changing the polymer dopant allows switchable devices to be fabricated. 13C NMR studies have been conducted on polyazulene.1 Diodes There has been an increased interest towards the possible applications of conducting polymers as the active elements in electronics [92-95].5 x 1020 and 5 x 1017 in doped and undoped polypyrrole samples. like metal-insulatorsemiconductor (MIS) diodes and p-n junction diodes [96-98].5. On interaction of a photon with a conducting polymer. Semiconducting polymers such as polyacetylene. refractive index and optical dielectric constants of a conducting polymer film [89]. The 13C NMR data obtained on the electrochemically prepared polypyrrole indicate the presence of α-α′ bonding in conducting polypyrrole films [88]. titanium. These conducting polymer films have been used for the fabrication of electrochromic and glucose biosensing devices [90. estimated as 1. The polyacetylene has been found to exhibit p-type behaviour when it is used for fabrication of Schottky diodes with low work function metals. polybithiophene and polyfuran in their respective doped and undoped states [87]. The ellipsometric technique has been used for the estimation of thickness. Besides this. Heterojunctions have recently been fabricated using electrochemically prepared polypyrrole and metal (indium. Schottky diodes formed between metallic AsF5– doped (CH)X and n-type GaAs indicate high electronegativity [99]. electrons get excited to a higher potential with concomitant creation of electron-hole pairs. aluminium and tin). 91].

the ideality factor and the barrier height of an indium/poly(o-anisidine) have been experimentally determined as 300. The values of the rectification ratio. estimated as 4. In.4972. 407 .Conducting Polymers in Molecular Electronics Figure 13. respectively. chronopotentiometery. It has been shown that the barrier height and the ideality factors determined are dependent on the work function of the metal used in the fabrication of these devices. Schottky devices have recently been fabricated by thermal evaporation of indium on polyaniline.41 and 0. SEM and FTIR techniques.49 eV. The improved ideality factor obtained as 1.10 Schematic diagram of a conducting poly(3-alkylthiophene) based Schottky device characteristics and hence the performance of these Schottky devices [100]. It has been recently revealed that it is possible to fabricate all vacuum deposited metal (Pb. From the results obtained using current-voltage measurements. Poly(3-methylthiophene) was prepared using an electrochemical technique to fabricate silicon-based devices [102]. respectively [103]. Al.2 for an Al/polyaniline/Ag device has been attributed to more intimate contact of the metal with the vacuum deposited polyaniline electrode. The observed deviation from the Schottky behaviour for these devices seen at higher voltages has been explained in terms of either the Poole-Frenkel effect or due to the presence of a large number of defects containing the trapped charges existing at the indium/poly (aniline-co-orthoanisidine) interface.42-4. The electrical characteristics of the junctions have been found to be dependent on the work function of polypyrrole. it has been seen that the rectifying behaviour was induced by covalent bond formation between poly(3methylthiophene) and the silicon. poly(o-anisidine) and poly(aniline-co-orthoanisidine). Sn)/polyaniline/metal Schottky devices [101]. 4.

54 for tin. respectively. Figure 13. like barrier height.11). 8. 6. The ideality factors of the CdSt2 layer/semiconducting polypyrrole structures have been estimated as 6.85. in comparison to the values of 8. aliminium and indium.57 and 6. 408 . of these devices were experimentally determined. rectification ratio and work function. the junction properties of Schottky devices using films of chemically synthesised poly(3-cyclohexylthiophene) and poly(3-n-hexylthiophene) units and metals have also been studied [104].20 obtained with a semiconducting polypyrrole interfaced with the same elements. Electrical properties of the poly(3-cyclohexylthiophene)/metal junctions were compared with those of the poly(3-n-hexylthiophene)/metal junctions (Figure 13. Better rectification properties of the poly(3-cyclohexylthiophene)/metal junctions were attributed to the decreased conductivity that perhaps results due to steric hindrance in the thiophene ring.Handbook of Polymers in Electronics Recently. It has been concluded that the passivation of the semiconducting polypyrrole results in the lower value of the ideality factor.82 and 8.63.11 Current-voltage and capacitance-voltage characteristics of metal/ conducting polymer junctions MIS structures were recently fabricated [105] by thermal deposition of metals (indium. Junction parameters. aluminium and tin) on Langmuir-Blodgett films of cadmium stearate (CdSt2) obtained on polypyrrole films electrochemically deposited onto ITO glass.

respectively.12 Schematic diagram of an ion-selective field-effect transistor. MIS field-effect transistors (MISFETs) and enzyme field-effect transistors (ENFETs) based on conducting polymers have also been fabricated. VD = drain voltage. ID = drain current 409 . Simultaneously. They have shown that this solid-state FET device is normally off (enhancement type) and the source (drain) current can be modulated by more than 102 by varying the gate voltage. VG = gate voltage.Conducting Polymers in Molecular Electronics 13.2 Field-Effect Transistor In conventional transistors.12. the conductivity of polymer changes. When charge is induced in the polymer layer by applying a voltage to the gate. This ‘field effect’ controls the current through a ‘gate’ electrode and thereby opens the possibility of transistor action without requiring the existence of p-n junctions. Janata and co-workers have investigated the electrical properties Figure 13. A schematic diagram of such a device is shown in Figure 13. After Koezuka. using electrical measurement technique. Tsumura and co-workers have fabricated a molecular electronic device based on an electrochemically prepared semiconducting polythiophene thin film [113]. many researchers applied various conducting polymers to construct field-effect transistor (FET) devices [109-111]. ‘field effect’ has been used to improve device characteristics [106]. they exploited thin film fabrication methods [112]. The application of field effect to fabricate conjugated polymer based device was first demonstrated by Koezuka and co-workers [108] using electropolymerised polythiophene. The transconductance and the carrier mobility have been estimated as 3 nS and 10-5 cm2 V-1 S-1.5. which in turn controls the drain current flowing between ‘source’ and ‘drain’. This phenomenon is useful not only for fabricating devices but also a very useful tool for studying semiconductor and surface states [107].

13). the device response is linear.13 ID-[conc. with increase in Cu(II) ion concentration was attributed to the conformational changes in the polymer matrix which arise due to the occupation of Cu(II) ions in the polymer matrix.] plot of an ion-selective microelectrochemical transistor The field-effect mobilities in these FET devices are found to be around 10-5 cm2 V-1 s-1 depending on the applied voltages and the nature of the gate insulator. Work on sexithienyl based FETs yielded more promising values. The increase in drain current. These values are significantly lower than that of inorganic semiconductor devices in which mobilities are found to be in the range of 0. Figure 13.Handbook of Polymers in Electronics of insulated gate field-effect transistors (IGFETs) using a chemically prepared polyaniline as a gate electrode [114].5 x 10-6 M Cu(II) ions and reaches a saturation region beyond 10-4 M Cu(II) ions (Figure 13. The response of the polyaniline insulated gate field-effect transistors (PANI-IGFETs) to step function potential has been experimentally determined.1-1 cm2 V-1 s-1 [116]. I D. The device turns on by adding 2. Saxena and co-workers [115] reported an ion-selective microelectrochemical transistor (ISMET) specifically responsive to Cu(II) ions using electrochemically prepared polycarbazole films. It has been found that the dc behaviour of these devices is the same as that of the corresponding MOSFETS (metal oxide semiconductor field effect transistors). the field-effect mobility reaching 3 x 10-2 cm2 V-1 s-1 410 . In the above concentration range.

which was a hundred times more than that measured using SiO2 [121].46 cm2 V -1 s-1 in cyanoethylpullulan (CYEPL) which is used as a gate insulator. The transducer can either be an electrical. 13. Waragai and co-workers reported a similar trend.. antibodies.5. A biosensor can be considered as a combination of an electrochemical or an electrical sensing device and a miniaturised reactor containing an immobilised biomolecule. the highest mobility recorded was 3 cm2 V-1 s-1 for dimethylsexithiophene (CMSxT) on CYEPL. Further. cells and receptors have been used as sensing probes for the fabrication of biosensors. Garnier and coworkers have reported fully plastic FET by using a printing technique [123]. It can be seen that conjugated polymers show a clear superiority over amorphous silicone if the cost is taken into account.3 Biosensors One of the most exciting areas of research in molecular electronics lies in the development of biosensing devices (usually called biosensors or receptrodes). The aim is to produce either discrete or continuous electronic signal(s) that is (are) specific to a single analyte (or a related group of analytes). i. A schematic of a biosensor is shown in Figure 13. Friend and co-workers demonstrated a high mobility conjugated polymer FET driving a polymer LED [125]. Nevertheless. the oxidation and reduction of electroactive substances. 119]. A number of biomolecules such as enzymes. A recently proposed device comprising of ‘polymer grid triodes’ by Yang and Heeger is worth noting [124]. Lately. organelles. whereas in amperometric biosensors current is based on heterogeneous electron transfer reactions. The potentiometric technique relates to the dependence of the potential on the analyte concentration.Conducting Polymers in Molecular Electronics [117]. The electrochemical method of detection has been at the centre of biosensor development. It was also found that an oligothiophene (sexithiophene) showed a mobility of 0. 411 . and is used in most cases to measure the concentration of a substrate. optical. lifetime and low response of the device restrict the competition of these materials with silicon-based devices. In the FET configurations. which is about one order of magnitude lower than that of an amorphous Si-based FET [118].14. The performances of conjugated polymer based FETs are quite encouraging and could be used to control a pixel in a liquid crystal display. the interface of the gate insulator and organic semiconductor layer plays a crucial role in charge transport [110. low-cost plastic electronics.e. the mobility being almost a thousand times higher than that measured using SiO2 as the gate insulator [120]. However. thermal or piezoelectric device. It is to be noted that these values of the mobility are comparable to or even surpass that of amorphous silicon [122]. the possibility of making a flexible panel with conjugated polymers opens a different field of large-area. The term has been defined as an analytical device incorporating a biological or biologically derived sensing element either integrated or intimately connected with a physicochemical transducer.

Different methods of immobilisation have been used. in the process. This is essentially a two-step procedure based on the formation of a functionalised conducting polymer film followed by the covalent binding of the enzyme at the functional groups on the polymer surface. Several conducting polymers can be deposited electrochemically and. selective and reliable information on the measurement species. (ii) that yield measurable signal.Handbook of Polymers in Electronics Figure 13. Immobilisation of biomolecules on the surface of an effective matrix with maximum retention of their biological recognition properties is a crucial problem for the commercial development of a biosensor. 132]. food industry. A number of reports have appeared on immobilisation of biomolecules using electrochemical entrapment [130. The application of conducting polymers in analytical chemistry has recently been reviewed [126-130]. Some of the other reasons that have made this area very attractive include those (i) that provide quick. 131. electrolyte salts. Another procedure for the immobilisation of biomolecules is the covalent binding of enzyme to a conducting polymer film. agriculture and environment industry. Some other reviews have been devoted to their use in design of biosensors [131.14 General principle of a biosensor Much interest in biosensors has been attached to the potential application of this highly expanding field of research to the solution of a variety of problems that occur in clinical diagnostics. Various publications in recent years indicate organic conducting polymers as a convenient tool for the immobilisation of enzymes at the electrode surface and its interaction with metallic or carbon electrode surfaces. (iii) that require minimum pretreatment of the samples. (iv) that are inexpensive and can be used repetitively. One such method is electrochemical entrapment. This is 412 . 136-143]. a biological molecule can be entrapped. This process is also useful in the fabrication of microsensors in preparation of a multilayered structure with one or more enzymes/biomolecules layered within a multilayered copolymer for analysis of multiple analytes [133-135]. The major advantage associated with this procedure lies in the independent optimisation of conditions required for the synthesis of the polymer with respect to solvent. film thickness and side reactions.

Cooper and co-workers have reported the electrochemical preparation of a glucose oxidase loaded polyaniline film [157]. poly(dichlorophenolindophenol) and overoxidised polypyrrole have also been elaborated [165-167] .. The glucose biosensor remains the most extensively studied biosensor. 157]. The Langmuir-Blodgett technique for monolayer deposition could be very successful in achieving the desired orientation of the molecule. Okhata and co-workers have used Langmuir-Blodgett films of GOD-stearic acid monolayers on a platinum electrode to fabricate an ultrathin glucose sensing membrane [174]. A full range of optical. A few biosensors based on insulating electropolymerised films like polyphenols. Some recent reports on polyaniline-glucode oxidase interaction include the work of Ozden and co-workers [168] and Karyakin and co-workers [169]. Bovine serum albumin and glutaraldehyde coupling [147] and various bifunctional reagents have been used to form a crosslinked network of enzyme. polyindole [137] and poly-o-aminobenzoic acid have recently been used for the fabrication of biosensors. etc. poly(o-phenylenediamine). 144-146]. Few reports have appeared on immobilisation in conducting polymers. Others report chemical grafting or affinity of the biomolecule at the functional group [152-155]. It has been found that polyaniline films exhibit enhanced loading of glucose oxidase after a self-exchange and hence can be used for the fabrication of third-generation glucose biosensors [37]. Lowe and coworkers [156] entrapped glucose oxidase in a polypyrrole matrix electrochemically deposited on a printed platinum electrode. Covalent coupling of an enzyme with a polymer can be carried out using carbodiimide coupling with the formation of peptide bonds [126. Besides this. such as antibodies [175-177]. with the crosslinking reagent on the surface of a conducting polymer [148-151]. have attracted much interest in the development of biosensors useful for detection of viruses and genetically transmitted diseases. Ramanathan and co-workers [171] have successfully used a physical adsorption technique to immobilise glucose oxidase in LangmuirBlodgett films of polyemeraldine base (PEB) deposited onto ITO glass. polyaniline [158-164]. Conducting polymers such as polypyrrole [127] and its derivatives [156.. Other biomolecules. enzyme) using an appropriate procedure in order to preserve the active state of the enzyme. electrochemical and piezoelectric transduction modes aimed at detecting the base pair hybridisation between the immobilised 413 .g. Morphological studies have revealed that the surface of a conducting polymer is critically dependent on the method of preparation [170] and plays an important role in the effective immobilisation of desired enzyme [171. DNA [178-180]. Few reports have appeared on this subject [173]. 172].Conducting Polymers in Molecular Electronics followed by immobilisation of the desired biomolecule (e. These GOD-PEB films have been seen to result in the linear increase of anodic current as a function of glucose concentration (5 to 50 mM). direct preparation of Langmuir-Blodgett films of GOD without the need to add a lipid layer has also been demonstrated by crosslinking with glutaldehyde.

Chaubey and co-workers have given a detailed account of the application of conducting polymers to biosensors in Chapter 10. and by disodium guanylate in mushrooms.Handbook of Polymers in Electronics cDNA probe and the target DNA have been developed. etc. 13. Taste comprises of five basic qualities: • • • • Saltiness produced by NaCl.5. Sourness produced by the hydrogen ions of HCl. Sussi and co-workers have designed 414 . carbon and gold electrodes has also been reported [181. fructose and sucrose. namely taste intensity and quality. The taste sensor employs the concept of global selectivity. Taste is perceived when the information on the substances is transformed into electrical signals that are transmitted to the brain via nerve fibre. caffeine. Mediated electron transfer reactions of DNA for detecting PCR (polymerase chain reaction) amplified genomic DNA and ferrocene mediated oligonucleotides for a sandwich-based electrochemical detection of DNA hybridisation have been described.4 Electronic Tongue Taste is produced when interactions between molecules and biological membranes are not specific to or characteristic of each molecule. The five kinds of basic taste qualities reflect the differences among these interactions. What is important in recognition of taste is not discrimination of minute differences in amounts of molecules but rather the transformation of molecular information contained in interactions with biological membranes into several kinds of groups. Deliciousness produced by monosodium phosphate and disodium inosinate in meat and fish. • Substances producing taste are received by the biological membrane of gustatory cells in taste buds on the tongue. The overall perception of taste is known to be due to a combination of taste senses and smell. and also called flavour or trigeminal sensor. Most wines contain about 8%-85% water and 500 other substances. and Sweetness due to glucose. Immobilisation of DNA onto glass. 182]. Wine has both taste and odour qualities due to the aromatic molecules in the liquid and vapour phases being different. acetic acid.. some of which are very important to the flavour in spite of low concentrations. L-tryptophan and MgCl2. citric acid. Bitterness produced by quinine. implying the ability to respond to many kinds of chemical substances at the same time.

i. versatility and robustness. working on the principle of pulsed voltammetry based on an array of five working electrodes. taste. the human olfactory system is very sensitive but not selective. The electronic tongues or taste sensors are based on the principle of potentiometry. A number of sensors for the measurement of odour and deliciousness based on conducting polymers are currently at various stages of technical development. defined as the ratio of the resistance change to the base resistance value. with global selectivity comprising of several kinds of lipid/polymer membranes for transforming information about substances producing taste into electrical signals. it is possible to miniaturise the taste sensor. The human nose neither tries to break the aroma into different constituents nor to quantify the constituents. The electrical resistance measured between different inner electrodes has been found to vary from 1 to 100 kΩ when volatile molecules are adsorbed at the surface of the conducting polymer film.e. there is no effective instrumental analysis to replace the human sense.. Polymerisation occurs when the monomer (25 mg) and the oxidising salt is sprayed onto four interdigited electrodes fabricated onto the alumina substrate. and clinical diagnosis. quality assessment for food. has recently been designed to follow the deterioration in the quality of milk due to microbial growth when milk is stored at room temperature [185].5 Electronic Nose The complicated olfactory system in humans and animals can detect and differentiate the presence of an odour even at trace levels [187]. Unfortunately. was estimated to be less than 2% for elements related to wine sensing. Typically. experience and mood. a taste-sensing fieldeffect transistor (TSFET) has recently been designed [186] for estimation of chemical substances in foodstuffs and organisms. A voltammetry technique has several advantages due to features such as very high sensitivity. However. Accordingly.Conducting Polymers in Molecular Electronics an odour-sensor array of different conducting polymers [183]. their use is 415 . as well as for the control of many cosmetics and fermentation processes [188-190]. Depending on the purpose and on the object to be measured. simplicity. the charging of the membrane is measured. high pressure liquid chromatography (HPLC) and NMR spectroscopy could be used to monitor the particular compounds present in a variety of samples. However. Toko [184] has fabricated a multichannel taste sensor.5. The average intensity. 13. wine and beverages. An electronic tongue. It appears that we are gradually entering into a new age of ‘food culture’. sensory evaluation in odour as well as food/ wine testing is performed by a panel of well-trained professionals based upon their sense of smell. Sensory evaluation is one of the important parameters for environmental monitoring. Analytical instruments such as gas chromatography (GC)/mass spectrometry (MS).

These devices operate at elevated temperatures (e. capable of recognising simple or complex odours [194]. They are easier to process than oxides. perfumery. αterpinethiol in water [191]. clinical diagnosis.g. 100-600 °C). The earliest work on the development of an instrument specifically to detect odour dates back to 1961. An electronic nose is often a bench-mounted instrument comprising of an array of electronic chemical sensors with partial specificity and an appropriate pattern-recognition system. which are sensitive but not selective. and so no heater is required.Handbook of Polymers in Electronics impractical for monitoring unknown odorous compounds. when Moncrieff reported a mechanical nose. and more importantly.. a lack of a direct correlation between the instrumental results and human perception. Consequently. the most interesting are conducting polymers. and spin casting. rapid. household products. such as in environmental monitoring.. There is low power consumption. screenprinting and Langmuir-Blodgett methods could be employed to fabricate sensors. quartz resonator and surface acoustic wave (SAW) devices have been proposed for the technical development of electronic nose for the analysis of vapours and different gases. food and drinks. • 416 . The processes suffer from tedious. there is an enormous demand for an electronic instrument that can mimic the human sense of smell and provide low-cost. tobacco and smoke. healthcare or pharmaceutical products.or nitrogen-based odours. They are highly insensitive to poisoning from sulfur-containing compounds. e. Organic polymers like polypyrrole can be readily patterned using standard integrated circuit technology. electrochemical. The polymer used can be made highly specific to chemical substances. However. Although there are some oxide materials that show a good specificity to certain odours. the term ‘electronic nose’ appeared around the late 1980s when one was demonstrated at a conference in 1987 [193]. there are several potential advantages to employing organic materials in an electronic nose. These sensors can be operated close to room temperature. The first report on an electronic nose was from Wilkens and Hatman in 1964 [192]. unlike tin-oxide sensors. mining. Of these materials. Several technologies such as tin oxide. They are quite sensitive to combustible materials such as alcohols but are generally poor at detecting sulfur. Conducting polymers are highly suited as odour sensing devices: • • • • • These sensors exhibit rapid adsorption and desorption kinetics at room temperature. time-consuming and expensive works.g. The electronic nose can be used to monitor and measure odour anywhere. These instruments probably cannot detect threshold (10-9 ppb) levels of some odorous compounds. sensory information.

An example is the Odour Mapper (UMIST Ventures. UK. The resistance of the sensor (arising due to the motion of charge carriers along the chains) varies with the changes in the concentration of the exposed vapours. has designed an electronic nose comprising of two conducting polypyrrole electrodes separated by 10 μm [198]. UK). It may thus be remarked that the polypyrrole sensors respond to vapours in a similar way. Attempts have also been made to use the polypyrrole nose to detect several other vapours such as isobutyl-3methoxypyrazine. These electronic noses are for specific purposes and there is presently no universal nose that can solve all odour sensing problems. isoalleraldehyde and methanthiol [199]. There is thus a wide scope for the development of an artificial nose. The size of the anion and the spacing between the polymer chains define how the solvent is dispersed around the chains. trichloroanisole. Similarly. Neotronics. The restriction to the electron flow when a trifluoromethyl molecule is attached directly to the polypyrrole chain is shown in Figure 13. that can mimic the human nose. which consists of an array of twenty conducting polymer chemoresistors. The anions diffuse between the chains due to the relatively weak interchain bonding of the polypyrrole whereas the cations form part of the chain.15 Profile of the variation in resistance with 10 different sensors for 4% ethanol solution 417 . There is thus a need to develop specific electronic nose technology appropriate for the application. based on conducting polymers. 196]. vanillin. The variation of change in resistance recorded from 10 sensors when exposed to a 4% ethanol solution is shown in Figure 13. The conducting polypyrrole is.Conducting Polymers in Molecular Electronics Different conducting polymers produce different responses when exposed to complex vapours [195. This means developing sensors. though not as effectively as the human nose. however. Figure 13. although some work on polyaniline has also been reported [197]. To date several electronic noses are available commercially or close to it. materials and appropriate pattern-recognition methods.16. the most commonly used.15.

In this context. drug-delivery and biosensing devices. It has been shown that it is possible to entrap conducting polymers in porous structures such as alumina. sol-gel films and polycarbonate membranes. optical and electrochemical properties of electrochemically synthesised polypyrrole within the pores of nanoporous polycarbonate filtration membrane walls [200]. Cyclic voltammetry. Entrapment of conducting polymers such as polyacetylene. it has recently been demonstrated that polyaniline can be electrochemically entrapped into the tetraethylorthosilicate (TEOS) matrix obtained on an ITO glass [205]. polyaniline and polythiophene in sol-gel films has recently been proposed [204]. Glucose oxidase and choline oxidase exhibit strong adsorption to these conductive layers obtained on gold electrodes. 418 .Handbook of Polymers in Electronics Figure 13.5. The application of conducting polymers as nanomaterials for electronic communication between redox enzyme and electrode surfaces is one of the active areas in biomolecular electronics. are promising candidates for molecular wires. linked by thiophene units of variable length.6 Nanowires Nanomaterials have been found to have several technological and commercial applications including use in electronic. thienoviologens.16 The restriction of electron flow in polypyrrole when trifluoromethyl molecule is attached directly to the polymer chain 13. 202]. optical. polypyrrole. In this context. UV-visible and IR spectroscopy and SEM studies have been used to detect the presence of electroactive polyaniline in a TEOS-derived sol gel matrix. Martin and co-workers have explored the electronic. Besides this. The results of these studies indicate that conducting polymers can be utilised as ‘molecular wires’. Malbers and co-workers [203] have shown that heteroarene oligomers comprising of two pyridinium groups. It has been suggested that organic microtubules can perhaps serve as a useful replica of various biological systems. these researchers have accomplished the template synthesis of a number of polymers on a nanoscale [201.

each with its own contacts and interconnections.Conducting Polymers in Molecular Electronics 13. using these materials as an emissive layer in LEDs [125. Conducting polymers have been considered to have outstanding potential for replacing inorganic light-emitting materials such as used in large area. Electroluminescence is the emission of light by electrical excitation. flexible displays. Although these technologies are trim and efficient compared with cathode ray tubes. These problems forced researchers to look for other materials. lightweight. They can be uniformly illuminated over a large area. the illuminated display is the primary energy consumer. As compared to conventional fluorescent materials. In many batteryoperated devices. They can be processed in the form of thin films and have potential for the production of flexible devices.e.5. Pope and co-workers [212] observed emission in single crystals of anthracene using silver paste electrodes at 400 V. cellular telephones and other hand-held instruments. it was established that the phenomenon of electroluminescence necessitates the injection of electrons from one electrode and holes from the other. backlit liquid crystal displays (LCDs) and vacuum fluorescent displays. Subsequently. the capture of one by the other (recombination) and the radioactive decay of the excited state (exciton) produced by the recombination process.. i. Output colours can span the whole visible spectrum. conducting polymers offer the following advantages: • The characteristics of conducting polymers can be altered either by modifying the electron structure or by chemically altering the polymer backbone. • • • • • 419 . Current flat-panel display technology primarily revolves around inorganic LEDs. such as laptop computers. LED displays are expensive to fabricate because of the many individual diodes required to make up an alphabet. The polymeric materials are available at low cost.7 Electroluminescent Displays The current interest in exploring the semiconducting properties of conducting polymers is for application to electroluminescence. they can be bulkier and much more power consuming than required for many applications. 206-211]. They operate with low dc voltage and are less power consuming compared to conventional LEDs or LCDs. Furthermore.

17).17 Relation between the structure of copolymers of 3-cyclohexyl thiophene and 3-n-hexyl thiophene. a number of conducting polymers have been produced that emit light across the visible spectrum and which may be used to fabricate devices with greater quantum efficiencies [31.01% (photons per electron) at Figure 13. Saxena and co-workers reported LEDs based on copolymers of substituted thiophenes [220]. The devices emit greenish-blue light in the wavelength region of 550-580 nm (Figures 13.19). 218] and fluorinated polyquinoline [219].Handbook of Polymers in Electronics Owing to the above advantages. which is easily visible in a poorly lighted room.18 and 13. Electroluminescence has been reported in different conjugated polymers such as poly (vinyl carbazole) (PVCZ). Red emission can be observed by the substitution of electron-donating groups at the 2. Poly (f-phenylene vinylene) (PPV) gives emission in the yellow-green region. 213-215]. Many efforts have been made to improve luminescence yields in conjugated polymers both through the use of copolymers formed with segments of the chain having different π-π* gaps and by the synthesis of higher purity polymers. The quantum efficiencies are in the range of 0. polyalkylfluorene [217.and 5-positions on the phenyl ring [216]. and the quantum efficiency of light-emitting didoes based on these copolymers 420 .002% to 0. The structures of the copolymer have been related to their electroluminescence property (Figure 13.

421 . (III) 1:1. Another approach to improve the performance is the use of additional semiconductor layers. These layers separate the emissive layer from the electrodes where undesirable non radiative recombination may occur. (III) 1:1.19 Electroluminescence spectra of copolymers synthesised using ratios of 3n-hexyl thiophene: 3-cyclohexyl thiophene (I) 1:9. and they also transport both carrier types to the recombination zone more efficiently [221]. (II) 2:3. (IV) 9:1 Figure 13. significantly higher than the corresponding values for poly(3cyclohexylthiophene)-based LEDs. (II) 2:3. (IV) 9:1 room temperature.Conducting Polymers in Molecular Electronics Figure 13.18 Photoluminescence spectra of copolymers synthesised using ratios of 3-nhexyl thiophene: 3-cyclohexyl thiophene (I) 1:9.

Alkyl Group CH3O CN Poly(3-alkoxy cyanoterephthalylidene) [239] OCH3 710 Red CN OCH3 1993 OCH3 422 .Handbook of Polymers in Electronics Table 13.1 Six processable and fluorescent conjugated polymers covering the entire visible spectrum Polymer Wavelength (nm) / Colour CH3O Repeating Unit OCH3 Year Poly(9-9.dihexylfluorene) [236] 427 Violet –O(CH2)3 CH CH CH CH 1991 OCH3 CH3O Poly(p-phenylene) [237] 465 Blue 1992 Poly(p-phenylene vinylene) [238] 477 Green 1990 Poly[2-methoxy-5(2′-ethylhexyloxy)-pphenylene vinylene] [216] O 590 Yellow OCH3 1991 R Poly(3-alkylthiophene) [217] 650 Orange 1991 S R .

8 Microactuators There is a considerable scope for the development of materials suitable for the fabrication of electromechanical actuators having very small dimensions. It is expected that many other problems like durability under drive and under storage conditions. It has been suggested that conducting polymers offer attractive alternatives for actuators that function more analogously to natural muscle. etc. degradation at the polymer-metal interface and the formation of dark spot defects. together with the co-intercalating solvating species. One hurdle is that different polymers are needed to emit light in different colours.1. along with several small entrepreneurial ventures.. These dimensional changes are largely due to the volume required to accommodate cations or anions. notebook computer screens. toys. with quantum efficiency over 4% [223]. One of the problems still confronting the technologists relates to the red-shifted blue emission in solid films of large-gap polymers including PPV-based ladder copolymers. Large-scale flexible displays. these conjugated polymers have been reported to exhibit light emission in the entire visible spectrum [222]. The six processable polymers covering the whole visible spectrum are summarised in Table 13. the potential for electroluminescent devices is enormous in. response time of 1 μs [224]. full colour polymer displays and luminescent room lighting are still a long way off.Conducting Polymers in Molecular Electronics To date. are attempting to grasp the huge market for electroluminescent displays. stereo equipment and automobile dashboard. Considerable progress has been made towards the understanding of the electronic processes that control the properties of the conducting polymer based electroluminescent diodes [228-231]. Recently. for example. radio receiver. (USA) and Cambridge Display Technology (UK). Conducting polymer electromechanical actuators are based on the large dimensional changes that occur from the redox doping of any of the host conducting polymers such as polypyrrole.5. small hand-held devices. Owing to their advantages. Many major companies such as Eastman Kodak. will soon get solved resulting in speedy commercialisation of the polymer electroluminescent displays. in the near future it appears that the two technologies will coexist until the market chooses the winner. brightness of about 106 cd/m2 [225] and device lifetime of 1000 hours [226]. large panel displays. roll-up TV screens. it has been shown that polymer displays can be fabricated using methods such as screen printing and ink-jet printing [227]. such as Uniax Corp. etc. Hewlett Packard and Phillips. and they come with a range of properties. Bolognesi and Botta have discussed in detail in Chapter 5 the application of polymers for light-emitting diodes. Microactuators are devices that convert electrical energy to mechanical energy. 13. The electrochemical actuators 423 . polyaniline and polyalkylthiophene [232]. However.

are futuristic. Thus conducting polymers are of greatest interest for either large actuators or microactuators using parallel arrays of thin electromechanical elements. the development of conducting polymer actuators is still in its infancy. Another advantage of conducting polymer lies in the fact that it is possible to use a conducting polymer actuator without an external source. an electrode that is anion doped can be reduced either during the addition of cations or the removal of anions. the cathode and the electrolyte.Handbook of Polymers in Electronics have direct similarities to both electrochromic displays and conducting polymer batteries. This is because fast response time can only be achieved using very thin electromechanical elements. Conducting polymers have also been utilised for fabrication of hydrostatic and extensional actuators. The net volume change is the overall volume change of the anode. Reversible electrochemical actuators comprise of an anode. stability 424 . It may be emphasised that many of the proposed applications of microactuators. other redox materials such as graphite have also been used as electromechanical electrodes. namely reproducibility. microtweezers and micropositioners. Either electrode or both can be conducting polymers. The dimensional changes can either be individual or relative changes in the dimensions of two or more elements. Kaneto and co-workers [233] have given (Chapter 8) an excellent review of conducting polymer based microactuators. The performance of conducting polymers is critically dependent on molecular diffusion. there are several problems associated with these materials. include microvalves. However. Compared to alternative actuator materials. Some of the shorter term goals. however. For instance. subsequent cycles would require external recharging. The hydrostatic actuators provide mechanical work using net volume change during electrochemical redox processes. which restricts the response of these actuators.6 Conclusions It has been shown that electrically conducting polymers are versatile electronic materials that display a unique range of properties for application to molecular electronics. However. a cathode and a separating electrolyte. The extensional actuators make use of either linear or biaxial changes in conducting polymers to obtain mechanical work. 13. The discovery that conducting polymer actuators can be operated at lower voltages indicates that these can be utilised for medical applications. such as microrobotics for exploration and repair of the human body to microscopic machines for the manipulation and alteration of micron dimensional objects. However. The nature of redox processes for conducting polymer electrodes has been found to be rate dependent. and the electromechanical cycle corresponds to both the chromatic switching cycle of an electrochromic display and the charge-discharge cycle of a battery.

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Handbook of Polymers in Electronics 440 .

7-diyl) Benzenesulfonic acid Conduction band Cholesterol oxidase Complementary metal oxide semiconductor Camphor sulfonic acid Chlorotrifluoroethylene Cyclic voltammagram Chemical vapour deposition Cyanoethylpullulan CTFE CV CVD CYEPL 441 .2-bithiophene-5.9-bis(3.5′-diyl 3-Octadecanoylpyrrole 3-Octadecylpyrrole Alternating current Auger electron spectroscopy Atomic force microscopy Aluminium 8-hydroxyquinoline 2-Acryloamido-2-methyl-1-propane sulfonic acid Atactic polystyrene (3-aminopropyl)trimethoxysilane Attenuated total reflectance Benzyl alcohol Bisacryloxybutyl tetramethyl disiloxane Poly(9.8-dioxaheptyl-fluorine-2.Abbreviations and Acronyms ηEL ηPL 3MOT 3ODOP 3ODP ac AES AFM Alq3 AMPSA aPS APTES ATR BA BABTDS BDOH-PF BSA CB ChOx CMOS CSA Electroluminescence efficiency Photoluminescence efficiency 3-methyl-4′-octyl-2.

2-Diazonaphthoquinone Discrete particle encapsulation Disperse Red 1 Differential scanning calorimetry Electron affinity Ethylene carbonate Electron-electron Electron-hole Electroluminescence Enzyme linked immunosorbant assay Electron nuclear double resonance Enzyme field-effect transistor Electrooptical Electron paramagnetic resonance Emeraldine salt Electron spectroscopy for chemical analysis Electron spin resonance Electron transporter layer Electric vehicle Flavin adenine dinucleotide Flavin adenine dinucleotide (reduced form) 442 .Handbook of Polymers in Electronics DBP DBS DBSA dc DEC DEZ DFWM DMF DNA DNQ DPE DR1 DSC EA EC e-e e-h EL ELISA ENDOR ENFET EO EPR ES ESCA ESR ETL EV FAD FADH2 Dibutylphthalate Dodecylbenzene sulfonate Dodecylbenzoyl sulfonic acid Direct current Diethylene carbonate Diethylzinc Degenerate four wave mixing Dimethylformamide Deoxyribonucleic acid 1.

Abbreviations and Acronyms FBP FET FIT FTIR FWHM GC GLDH GOD GPC HMDSO HOMO HPC-Py HPLC HRP HSA HTL I(t) IC IEEE IGFET IP IPS IR ISC ISFET ISMET IT ITO KC8 LB Fluorinated polymethacrylate Field-effect transistor Fluctuation induced tunnelling Fourier transform infrared Full wave half maximum Gas chromatography Glutamate dehydrogenase Glucose oxidase Gel permeation chromatography Hexamethyl disiloxane Highest occupied molecular orbital Pyrene-labelled hydroxypropylcellulose High pressure liquid chromatography Horseradish peroxidase Human serum albumin Hole transporter layer Emission intensity Internal conversion Institute of Electrical and Electronics Engineers Insulated-gate field-effect transistor Ionisation potential Isotactic polystyrene Infrared Intersystem crossing Ion-selective field-effect transistor Ion-selective microelectrochemical transistor Information technology Indium tin oxide Potassium graphite Langmuir Blodgett 443 .

4-phenylenevinylene] Metal-insulator Metal-insulator semiconductor Metal-insulator semiconductor field-effect transistor Mevalonic lactone methacrylate Multilayer resist Poly(2.5-dimethoxy-p-phenylene vinylene) Metal oxide semiconductor field-effect transistor Magnetoresistance Microresists Mass spectrometry Methyltetrahydrofuran Microwave Mach-Zehnder Nicotinamide adenine dinucleotide Nicotinamide adenine dinucleotide (reduced form) n-BCMU-PDA n-Butoxycarbonylmethyl urethane 444 .Handbook of Polymers in Electronics LC LCD LCST LDH LDM LED LOD L-PPP LS LUMO MAdMA MC ME MEH-PPV M-I MIS MISFET MLMA MLR MOPPV MOSFET MR MRS MS MTHF MW MZ NAD NADH Liquid crystalline Liquid crystal display Low critical solution temperature Lactate dehydrogenase Laser displacement meter Light-emitting diode Lactate oxidase Ladder PPP Leuco-emeraldine salt Lowest occupied molecular orbital 2-Methyl-2-adamananol methacrylate Magnetoconductance Molecular electronics Poly[2-(2´-ethylhexyloxy)-5-methoxy-1.

4-dialkyl-2.2′-bithiophene) Poly(9.4-di(2-thienyl)benzene Polyemeraldine base Poly(3.9-di(ethylhexyl)fluorine Poly(1.Abbreviations and Acronyms NLO NMP NMR NSOM ODMR OMA P(PMMAOM-MAN) P/GC/MS PAAM PAB PAN PANI PaS PAT PAV PBI PBS PC PCM PCz PDA PDABT PDF2/6 PDTB PEB PEDOT PEI PEO PET Non linear optical N-methyl-2-pyrrolidinone Nuclear magnetic resonance Near-field scanning optical microscopy Optically detected magnetic resonance Organised monolayer assembly Poly(methyl methacrylate-co-3-oximino-2-butanone methacrylate-comethacrylonitrile) Pyrolysis/gas chromatography/mass spectroscopy Polyacrylamide Poly(o-aminobenzoic acid) Polyacrylonitrile Polyaniline Pernigraniline salt Polyalkylthiophene Poly(arylene vinylene) Polybenzimidazole Phosphate buffer saline Propylene carbonate Portable conformable masking Polycarbazole Polydiacetylene Poly(4.4-ethylenedioxythiophene) Polyethyleneimine Polyethylene oxide Polyethylene terephthalate) 445 .

6-diol] Polythienylene vinylene Polyvinyl chloride Polyvinylcarbazole Physical vapour deposition 446 .9.6-dimethylphenylene oxide) Poly(p-phenylene) Polyphenylenediyl-pyridinediyl Poly(p-phenylene vinylene) Polypyrrole Polystyrene Polystyrene sulfonated acid Polyurethane with symmetrical substituted tris-azo dye with fluorinated alkyl units Polythiophene Polythiophenediyl-bipyridenediyl 3.10-Perylene tetracarboxylic dianhydride Polythiophenediyl-pyridinediyl p-Toluene sulfonate Poly[bis(p-toluenesulfonate) of 2.Handbook of Polymers in Electronics PFu PHP PI PL PMAN PMeT PMMA PNIPAM PNMA PP/VD PPMA PPO PPP PPPY PPV PPy PS PSSA PSTF PT PTBPY PTCDA PTPY PTS PTS-PDA PTV PVC PVCZ PVD Polyfuran Para-hexaphenyl Polyimide Photoluminescence Poly(o-methoxyaniline) Poly(3-methyl)thiophene Polymethyl methacrylate Poly(N-isopropylacrylamide) Naphthyl-substituted polymethacrylate Plasma polymerisation/vapour deposition Poly(phenyl methacrylate) Poly(2.4-hexadiyne-1.4.

Abbreviations and Acronyms PVdF PVN PVP PVS q-1D QCM QPM RDM RF RGB RIE SA SAW SBAC SCE SEI SEM SHG SPIE SPM SPR SSH StA STM T-BOC T-BOC-PMS TCNQ TCR TEM TEOS Polyvinylidene fluoride Polyvinylnaphthalene Polyvinylpyrrolidine Polyvinylsulfonate Quasi one-dimensional Quartz crystal microbalance Quasi-phase-matching Random dimmer model Radio frequency Red green blue Reactive ion etching Salicyclic acid Surface acoustic wave Symmetrically substituted benzylidene aniline with chloride Standard calomel electrode Solid electrolyte interface Scanning electron microscopy Second-harmonic generation International Society for Optical Engineering Self phase modulation Surface plasmon resistance Su Schrieffer and Heeger Stearic acid Scanning tunnelling microscopy t-Butyl carbonate Poly(p-t-butyloxycarbonyloxystyrene) Tetracyanoquinodimethane Temperature coefficient of resistance Transmission electron microscopy Tetraethylorthosilicate 447 .

2-(4-(pethylphenyl))triazole Taste-sensing field-effect transistor p-Toluene sulfonate Tetrathiafulvaline Transistor-transistor logic Ultraviolet photoelectron spectroscopy Ultraviolet Valence band Very large scale integration Onset voltage Vibrational relaxation Variable-range hopping Weak localisation X-ray photoelectron spectroscopy X-ray diffraction ?-Butyrolactone ?BL 448 .20-(10.13)-didecyl)distyrylbenzene-co-1.Handbook of Polymers in Electronics Tg TGA THF THG TMT TOF TPD TRIDSB TSFET TSO TTF TTL UPS UV VB VLSI Von VR VRH WL XPS XRD Glass transition temperature Thermogravimetric analysis Tetrahydrofuran Third-harmonic generation Tetramethyltin Time of flight Triphenylamine derivative Poly(1.

Bassini 15 20133 Milano Italy Asha Chaubey Biomolecular Electronics & Conducting Polymer Research Group National Physical Laboratory Dr K. Bassini 15 20133 Milano Italy C.Contributors S.1er et Case 185 4 Place Jussieu. Krishnan Road New Delhi-110012 India Jean-Claude Dubois Université Pierre et Marie Curie Laboratoire de Physico-chimie des Polyméres Tour 44. 75252 Paris Cedex France 449 .S. Annapoorni Department of Physics and Astrophysics University of Delhi Delhi – 110007 India Alberto Bolognesi Istituto di Chimica delle Macromolecole Consiglio Nazionale delle Ricerche Via E. Botta Istituto di Chimica delle Macromolecole Consiglio Nazionale delle Ricerche Via E.

.Handbook of Polymers in Electronics Anamika Gambhir Biomolecular Electronics and Conducting Polymer Research National Physical Laboratory Dr. Miyagi 980-77 Japan Masmitsu Kaneko Department of Computer Science and Electronics Kyushu Institute of Technology Iizuka. Krishnan Road New Delhi – 110012 India Manju Gerard Department of Chemistry Allahabad Research Institute (Deemed University) Naini Allahabad-210007 India Atsunori Hiratsuka Health Care Group Living Environment Development Center Matsushita Electric Industrial Co. 3-1-1 Yagumo-naka-machi Moriguchi City Osaka 570-8501 Japan Toshikuni Kaino Institute for Chemical Reaction Science Tohoku University 2-1-1 Katahira Aoba-ku Sendai-shi. Fukuoka. 820-8502 Japan Keiichi Kaneto Department of Computer Science and Electronics Kyushu Institute of Technology Iizuka. Ltd. K. Fukuoka. 820-8502 Japan 450 .S.

Krishnan Marg New Delhi-110012 India Reghu Menon Department of Physics Indian Institute of Science Bangalore India – 560012 Amalesh Mukhopadhyay Department of Science and Technology New Mehrauli Road New Delhi – 110016 India K. Malhotra Biomolecular Electronics & Conducting Polymer Research Group National Physical Laboratory Dr K. Narayan Chemistry and Physics of Materials Unit Jawaharlal Nehru for Advanced Scientific Research Jakkur PO Bangalore 560064 India Tim H.Contributors Isao Karube Karube Laboratory Biosensor Division Research Centre for Advanced Science and Technology University of Tokyo 4-6-1 Komaba Meguru-ku Tokyo 153-8904 Japan Bansi D.S. Richardson Applied Molecular Engineering Group Department of Physics & Astronomy University of Sheffield Hounsfield Road Sheffield S3 7RH UK 451 .S.

Krishnan Road New Delhi – 110012 India Barbara Wandelt Technical University of Lodz Faculty of Chemistry Department of Molecular Physics Zeromskiego 116 90924 Lodz Poland 452 . K.S. Krishnan Road New Delhi – 110012 India Bruno Scrosati Department of Chemistry University ‘La Sapienza’ 00185 Rome Italy Rahul Singhal Biomolecular Electronics and Conducting Polymer Research National Physical Laboratory Dr.Handbook of Polymers in Electronics Vibha Saxena Biomolecular Electronics and Conducting Polymer Research National Physical Laboratory Dr. K.S.

267 affinity biosensors 289-290 Ag/AgCl electrode 319 Alexandrium affine 289 alkanethiol-stabilised metal nanoparticles 357 alkanoic acid 383 alkoxy substituted PPV 169 3-alkyloxymethoxy thiophene 76 3-alkyl-substituted thiophenes 345 3-alkylthiophene 164 Alq3 see aluminium 8-hydroxyquinolene (Alq3) alternate layer Langmuir trough 385. electroluminescence 141 aluminium 370 3-aminopropyltriethoxysilane 352 3-aminopropyltrimethoxysilane (APTES) 289 2-aminopyridine 106 amperometric biosensors 301. 256 azo-dye-functionalised main-chain polymer synthetic scheme 79 χ(3) wavelength dependence 80 azo-dye-functionalised poled polymers 84-87 azo-dye-functionalised polymer waveguides 90-93 azo-dye polyester 76 453 . 367 antibodies 413 ArF 197. 317 electron transfer in 303-304 response measurements 319 anisotropy conductivity 53 electroluminescence 169 electrolytic expansion in polyaniline films 266 etching techniques 190 anode 370. 405 attenuated total reflectance (ATR) 283 Au-P30T 358. 200 aromatic hydrocarbons 104 Arrhenius relation 311 artificial muscles 255 arylene-bisphosphylidenes 148 atactic PS (aPS) 123-125 atomic force micrograph (AFM) 404. 303. 111 acetone 398 acid-amine ion linkage 210 acid anhydride bonds 204-205 acid photogenerators 199 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPSA) 48 acrylate ester 209 actuators 255. 371 anthracene 121. 360 AX 1000 photoresist 201 AZ Electronic Materials 201 azo benzene 255. 386 alternate layer LB deposition technique 385 alternate layer LB films 386 aluminium 8-hydroxyquinolene (Alq3). 313.Main Index Index A absorbance 372 absorption 100.

309. 287. 394.8Co0. 413 healthcare 318 importance of conducting polymers 302-304 key attraction 297 market 298 medical diagnostic application 297 microbiosensors 276 non medical application market 297 optical 314 potential applications 412 potentiometric 301. 411-414 1st generation 300 2nd generation 300 3rd generation 300 4th generation 300 amperometric see amperometric biosensors blood glucose 298 cholesterol 323-324 classification 313 conducting polymer-based 297 conductometric 315 construction 299-300 design 412 development 297. 243-245 lithium-ion 217. 230-231 rocking chair 230-231 SnO2/LiClO4-EC-DMC-PAN/ LiNi0. 395 band structure 4.3. 146 bifunctional device 356 bifunctional reagents 307 bimolecular photophysical processes 103-104 bimolecular photoprocesses 110 bimorph actuator 257 binder 272 biocomponents 301-302 biological fluids. 411 selectivity 301 sequence of events 299-300 specificity 301 types 313-317 2-(4-biphenyl)-5-(tert-butylphenyl-1.2 O2 237 BDOH-PF 163 benzene 112. 315 fabrication 413 general principle 412 generations 300 glucose 318.4oxadiazole (PBD) 158 bipolaron 4. 315-317 research and applications 297-300 response measurements 313 schematic 299. 396 energy levels and occupied localised states 11 454 . 275-276. 6. immobilisation 305-309. 142. 116 benzenesulfonic acid (BSA) 260 benzyl alcohol (BA) 123 benzylidene aniline 77 β-carotene 376. 377. 298 effects of storage time 312-313 electrochemical 313. 412-413 biosensors 272-273. 9-12.Handbook of Polymers in Electronics B backscattering lifetime 41 band gap 5. analysis 297 biological parameters 297 biomedical applications 272 biomimetic actuators 255 biomolecules. 5 batteries C/LiMO2 polymer lithium-ion 244 high energy density 217 Li-AyBz lithium 221 Li/LiClO4-EC-DMC-PAN/LiCryMn(2y) O4 235 Li/PEO-LiCF3SO3 + çLiAlO2/LiMn2O4 225 lithium 218-239. 403 bias voltage 144. 148.

3-bis-1-naphthylpropane 116 1. 118. 113. end-face 92-93 butraldehyde 275 Buttiker-Landaur conductance formula 26 catalytic biosensors 287-288 cathode 370 centralised testing 297 chain conformation effect on excimer emission 122-126 chain densification effect 113 chain interaction 9 chain interruptions 21 chain length 112-113 chain orientation 13. 146. 357 cadmium sulphide (CdS) 341. 107. 11 instability 17 interchain transport 20 negative 11 1.3-bis-2-naphthylpropane 116 bis-acryloxybutyl tetramethyl disiloxane (BABTDS) 208 bisazide 196. photophysics 346-360 charge transfer excitons 143 charge transfer process 4.Index formation 9. 119 association of 103 (CH)x-FeCl3 42 C C NMR studies 406 C60 343 cadmium selenide (CdSe) 341. 353. 169 chain scission reactions 119 chalcogenide glass fibre 84 channel waveguides 75. 398 polynaphthyl methacrylate in 111 chloroform-cyclohexane 112 chloromethylated polystyrene 203 chlorophyll 376 cholesterol biosensors 323-324 chromophores 99. 87 charge carriers 375 charge-discharge cycle 238 charge-discharge process 242 charge generation and separation 346347 charge injection 143. 115. 124. 201 blood glucose biosensor 298 bobbin-type configuration 231 Boltzmann constant 21 Boltzmann distribution 107 bovine serum albumin 413 branched side chains 150 breakdown voltage 227 Brillouin zone 5 2-bromoethylamine 275 buried waveguide. 394 charge transfer TTF:TCNQ-type molecules 379 charge transport 3-36. 146. 143 chemical sensors 287 chemical vapour deposition (CVD) 276 chloroform 112. 348. 353-355 calcium 370 camphor sulfonic acid (CSA) 38 capacitance-voltage characteristics 408 carbazole 107 carbon-carbon bonds 112 carbon-carbon distance 41 carbon-carbon double bonds 375 carbon-carbon single bonds 375 carbon nanotubes 267 carboxylic acid 195 carrier density 377 carrier mobility 375 carrier transport 369 13 455 . 406 charge transport carriers 6-12 charge transport models 18-27 chemical doping 4. 148 charge separation 349 charge separation nanoparticle-polymer systems.

343. 286 applications 403 properties 403 conducting polymers 1. 18. 142143 conductivity see electrical conductivity conductometric biosensors 315 configuration co-ordinate 7 conformation change of PPMA 113 conformation effect of polymer chain 110-118 conjugated polymers 1.Handbook of Polymers in Electronics (CH)x-I2 42 cis-polyacetylene 3. 395 synthesis 304. 397 magnetic susceptibility 56-58 molecular devices based on 406-424 specific heat 56-58 structures 378. 395 cis-1. 6. normalised resistivity (ρ) versus temperature 43 ClO4--doped polyacetylene 14 coatings 272 coin-type cell configuration 234 collapse transition 126-135 collisional energy transfer 118 colour components 376 colour purity 371. 11 Coulomb potential 16 covalent binding 308. 342. 412 covalent bonding 307 critical states 58-63 crosslinking 307 through anhydride 204-205 456 . 397-399 see also specific types and applications conducting properties 3-4 conduction band 4. 375-378 analytical chemistry 412 applications 397 as odour sensing devices 416-417 band gap 395 biosensors 297-239 characterisation 397. 367. 255. 257. 5. 261 contraction ratio of polyaniline films 267 COP 206. 217. 404-406 characteristics 419 charge transport models 18-27 conduction mechanism 305 electrical transport properties. 373 enhancement 374 complementary metal oxide semiconductor (CMOS) circuits 284 concentration quenching 103 conducting films 271. 16. 10. 5. 207 core channel waveguide 88 core-shell synthesis 341 Coulomb interaction 9. 375 anisotropic electrical and optical properties 142 band gap 148 charge transport 3-36 light emission in entire visible spectrum 422-423 physical properties 397 physics of 142-144 preparation methods 344-346 synthesis 151 conjugation length 376 consumer testing 297 contraction ratio 260. summary 63-65 electrolytic expansion 267-268 in molecular electronics 393-439 applications 394.4-polyisoprene 196 cis-trans photoisomerisation 255 Clariant Corporation 201 C/LiClO4-EC-PC-PAN/LiCryMn(2-y)O4 234 C/LiClO4-EC-PC-PMMA/PPy 244 C/LiMO2 polymer lithium-ion batteries 244 ClO4-(CH)x 43 ClO4-doped polyacetylene.

141. 259. 12. 260 cyclised polyisoprene 203 3-cyclohexyl thiophene 420.6dioxaheptyl)fluorene 163 dichloro-p-xylene 149 dielectric materials 271 dielectric relaxation 404 N. 133 Cu(II) ions 410 current density 375 current-voltage characteristics 371. 229 power law behaviour 58 temperature dependence 41. 41.N-diethylaminonitroazobenzene 79 diethylzinc (DEZ) 285 differential scanning calorimetry (DSC) 123. 242.9-bis(3.7-dibromo-9.2-diazonaphthoquinone (DNQ) 193 photodecomposition 194 diblock copolymers 346 2.Index crosslinking centres 223 crystal-crysal transition 134 crystalline iPS 123-125. 257. Birks’ scheme 103 decentralised testing 297 deep-UV photoresists 197 degenerate state 7 delayed emission 111 delayed fluorescence 102. 408 cyano-PPV 157 cyanothylpullulan (CYEPL) 411 cyclic voltammogram (CV) 257. 143. 40-49. 421 dimethylsexithiophene (CMSxT) 411 diodes 406-408 dipole-dipole interaction 118 discharge-charge cycle 237 discrete particle encapsulation (DPE) 345 disorder 9. 260. 262 diffusion constant 257 E elastic scattering 41 electrical conductivity 21. 377. 131. 305. 393. 397 diffraction efficiency of waveguide grating 91 diffusion coefficient 41. 50 influence on transport properties 1415 disordered metallic regime 41 DNA 413-414 immobilisation 325 DNA biosensors 324-325 DNA sensor 290 dodecylbenzene sulfonate (DBS) 324 dodecylbenzoyl sulfonic acid (DBSA) 38 dopant-chain interaction 16 doping 4. 397. 110 density of states 16. 190. 370 dual lithium ion 244 D data acquisition system 105 data analyser 105 deactivation. 372. 57 DFWM 76 1. 396. 394. summary 63-65 electric field 377 intensity 11 poling technique 87 457 . 46 electrical properties of doped conjugated polymers 37-68 electrical transport properties of conducting polymers. 396 anisotropy 53 Arrhenius plots 224. 404 influence on transport properties 1516 double-layer LED 158 down-chain energy migration 118 DR1 92 drive voltage 369.

412 electrochemical oxidative polymerisation 398 electrochemical stability 227 electrochemical synthesis 167 electrode-less microwave or high frequency reactors 280-281 electrodes 369 preparation 304-305 electroluminescence 166. 370 polarised 168-170 polymer 368-374 electroluminescence response 354 electroluminescence spectra 421 electroluminescent devices physics of 142-147 potential for 423 electroluminescent displays 419-423 electrolytic capacitors 274 electrolytic deformation 256 measurements of 257 electrolytic expansion 256 anisotropy of. 166. 142 electron-energy-loss spectroscopy 11 electron-hole (e-h) pairs. 347 aluminium 8-hydroxyquinolene (Alq3) 141 anisotropy 169 efficiency 145. 242-245 electronic encapsulation 284 electronic excitation energy 118 electronic ground state 4-6 electronic nose 415-417 electronic tongue 414-415 electron magnetic resonance spectroscopy 8 electron nuclear double resonance (ENDOR) 8 electron paramagnetic resonance (EPR) spectroscopy 23 electron-phonon coupling constant 21 electron-phonon interactions 4. 170 little or no 371 measurement 348 organic 367. 6. 369. 53. recombination of 371 electron-hole (e-h) separation 142 electron-hole (e-h) transporter 167 electronically conducting polymers 217. 273 electron correlation 6 electron-electron (e-e) interactions 4-6. 159. 52. 157. 161. 150. 13.Handbook of Polymers in Electronics electric vehicles (EV) 217 electrochemical biosensors 313. 142 electron-phonon scattering 13 electrons 24 electron spectroscopy for chemical analysis (ESCA) 282. in polyaniline films 266 applications 268-269 measurement of 258 pH dependence of 262 time response of 265 electrolytic expansion in conducting polymers 267-268 electromechanical actuators 423 electron-beam irradiation 205 electron-beam lithography 186 electron-beam resists 202-206. 404 electron transfer in amperometric biosensor 303-304 electron transporter 158 electro-optical (EO) materials 86-87 electropolymerisation 308 electropolymerised conducting films 313 ellipsometric technique 406 EL-V (EL intensity versus bias voltage) 147 emeraldine salt (ES) 260 458 . 315 electrochemical doping 4 electrochemical entrapment 307-308. 283 electron spin resonance (ESR) 16. 168. 5.

373 emitting layers 369 emulsion polymers 272 encapsulation 371 end-to-end cyclisation 117 energy band diagram 396 energy bandgap 376 energy gap 3. 118-121 efficiency 118 fluorescence measurements of 121 types 118 environmental monitoring 326 enzyme acitivity. dependencies of 260262 extensional actuators 424 external electrode reactors with RF power supply 280 F FeCl3-(CH)x 43 FeCl3--doped polyacetylene 14 FeCl3 polymerisation 167 Fe2O3 344 Fermi energy 13 Fermi level 4. thin films. iPS gel 129 excimer formation 115 effect of temperature 115 molecular weight effects on 113 excimer photophysics for two-phase system 133 excimers 103. 56. determination of 309310 enzyme activity profile 311 enzyme electrodes 309-313 enzyme field-effect transistors (ENFETs) 409 enzyme immobilisation 304-309 enzyme-immobilised electrode 274 enzyme linked immunosorbant assay (ELISA) 326 enzymes 302. 375. 145 Fermi velocity 41 ferrocene carboxylic acid 319 ferrocene-modified siloxane polymers 275 field-effect mobilities 410 field-effect transistors (FETs) 379. 376. 104. 143 excitation. ultrathin films and specific types flavin adenine 307 459 . 57. 191 ethyl acetate 112 ethylene carbonate (EC) 222 excimer dissociation 115 excimer emission 113 chain conformation effect on 122-126 excimer fluorescence 106-135.Index emission efficiency 148 emission spectrum 371 emission wavelength 373 emitter materials 371. 395 energy migration coefficient 126 energy migration processes 118-121 energy migration studies 109-110 energy storage and conversion 217 energy transfer 110. 143 exciplexes 104. 4. 409411 field-induced transition 61 W versus temperature 60 films see conducting films. effect of temperature 311-312 enzyme activitiy. 303 optimum pH 310-311 enzyme support system 287 etching 190. 101 excited triplet state 100 exciton generation 146 excitons 347-348 exciton trap 109 expansion ratio. 111 excimer fluorescence lifetimes. 5. Birks’ scheme 103 excitation energy 119 excited singlet state 100.

421 high energy density batteries 217 high pressure liquid chromatography (HPLC) 415 hole transporter 158. 376 hopping/tunnelling transport 24 Hubbard model 5.4-heptadiene 397 heteroaromatic polymers 76 molecular structure of 80 χ(3) wavelength dependence 82 heterojunctions 406 hexamethyldisilazane 284 hexamethyldisiloxane (HMDSO) 284. 101. 287288.Handbook of Polymers in Electronics flavin adenine dinucleotide (FADH2) 275 Flory theory 111 fluctuation induced tunnelling (FIT) model 23-25 fluorescence 100. 111 decay 125 definition 101 delayed 102. 109. 207 GOD-PEB films 413 GOD-stearic acid monolayers 413 gold nanoparticles 346. 110 investigations 99 lifetimes 105 ‘normal’ 102 of polymers 106-135 in gel state 122-135 in solution 110-121 study methods 105 fluorescence emission spectrum for iPS gel 132 fluorescence measurements of energy transfer 121 fluorescence probe method 99-100 fluorescence spectra 111 of phenyl methacrylate 114 of poly(phenyl methacrylate) 113-115 fluorescence spectroscopy 105 fluorinated polymeric ethers 274 fluorinated polymethacrylate (FPB) 207 sensitivity curve 207 fluorinated polyquinoline 420 fluorosphores 341 food industries 297 Frenkel exciton 143 Fresnel reflection loss 89-90 Frohlich conductivity 6 gel-type electrolytes 227-229 configuration 226 glass transition temperatures 86 glow discharge 277 glucose biosensors 318. 232 gel state. fluorescence of polymers in 122-135 460 . 169 HOMO (highest occupied molecular orbital) 144-145. 6 Huckel model 15 humidity content 241 humidity sensors 287 hybrid waveguides 93-94 hydrochloric acid etchant 371 G GaAs 285 gas chromatography (GC)/mass spectrometry (MS) 415 gel electrolytes 230. 275. 297. 357-360 gold-polythiophene blends 357-360 GPC 404 graphite anode 233 ground state energy 7 H 1. 413 glucose oxidase (GOD) 274. 290 3-n-hexyl thiophene 420. 318 glutamate dehydrogenase (GLDH) 314 glutaraldehyde 413 GMC 206. 287. 317.

151. 103 intramolecular excimer formation 117 iodine 394 iodine-doped polyacetylene 19. 41 inelastic electron-phonon scattering 45 inelastic scattering 41 information technology 69. 13 iodine-doped Tsukomoto (CH)x 37 ion-beam lithography 186 ionically conducting polymers 217-242 ionic attraction 387 ion-selective field-effect transistor (ISFET) 273. 371. 131. 413. 141 conductivity (both parallel and J Jablonski diagram 100 461 . 159. 367 inorganic nanoparticles 346 insulated gate field-effect transistors (IGFETs) 410 insulating states 58-63 insulators 284-285 interchain coupling. 170. 143 interchain transfer 16 interface materials 272 internal conversion (IC) 100-102 internal electrode reactors with dc power supply 280 with RF power supply 280 intersystem crossing (ISC) 100.Index hydrostatic actuators 424 8-hydroxyquinolene (Alq3) 168 electroluminescence of aluminium 141 4-hydroxystyrene 200. 44. 353. 201 perpendicular) versus temperature 45 resistivity versus temperature 44 iodine-doped trans-polyacetylene 3. 287. 45 immobilisation biomolecules 305-309. 133 density measurements 129 excimeric fluorescence lifetimes 129 extended conformation 128 fluorescence decay parameters 128 fluorescence emission spectrum 128 steady-rate fluorescence emission spectrum 132 time-resolved fluorescence emission spectra 131 IR spectroscopy 283 ISC see intersystem crossing (ISC) isobutylene 200 isotactic polystyrene see iPS ITO 144. influence on transport properties 17-18 interchain hopping 19 interchain interactions 4. 101. 412-413 DNA 325 enzyme 304-309 methods 305-309 immunosensors 326 imprinted polymers 271 impurity potentials 16 indium tin oxide see ITO inelastic electron-electron scattering 13. 418 ITO/BDOH-PF/Ca 163 ITO-coated glass 141 ITO/PPV/Al 150 ITO/PPV/cyano-PPV/Al 158 ITO/PVCZ/alkoxy PPP/Ca 161 I-V (current intensity versus bias voltage) 147 I I-(CH)x 43. 42. 409 ion-selective microelectrochemical transistor (ISMET) 410 iPS/BA gel 126 time-resolved fluorescence emission spectra 130 iPS gel 123 crystalline 123-125.

168. 408. 127 light emitting diodes see LEDs light-emitting polymers 367 Li/LiClO4-EC-DMC-PAN/LiCryMn(2-y)O4 battery 235 Li2MnO4 235 LiMn2O4 231 lineweaver-Burke plot 321 LiNiy Co1-yO2 231 Li/PEO-LiCF3SO3 + γLiAlO2/LiMn2O4 battery 225 Li/(PEO)20LiI-EC-Al2O3/FeS2 cell 224-225 LiPF6-EC-DMC 232 LiPF6-EC-DMC-PAN 225 LiPF6-EC-PC-PAN 227. 229. 237 LiClO4-PC 243 LiCoO2 231 LiCoO2 cathode 236 LiCryMn(2-y)O4 electrode 234 lifetime parameter 105. 223 Li+ cations 219 Li+ ion 223 Li-AyBz lithium battery 221 LiClO4 220 LiClO4-EC-DMC-PAN 232-234. 199. 401 laser power and SHG efficiency 90 layer-by-layer polyelectrolyte selfassembly process 387 LCST see lower critical solution temperature (LCST) least-squares analysis 105 LEDs 141-183. 195 KrCl 197 KrF 197 L lactate biosensors 321-322 lactate dehydrogenase (LDH) 312. 357. 419 462 . 367. 413 applications 403-404 pressure-area isotherm 400 Langmuir-Blodgett technique 159.Handbook of Polymers in Electronics K Kerr switch 83 Kivelson and Heeger model 16 KPR resist 194. 381. 308. 321-322 lactate/pyruvate substrate recycling 322 ladder PPP (L-PPP) 161 Landau-Ginzberg model 17 Langmuir-Blodgett deposition 381. 419421 characterisation 147-148 complex polymeric structures used as active materials 154-157 degradation 170 double layer 158 lifetime 170 mechanisms involved 147 microcavities 170-171 narrowing of emission spectrum in microcavity 171 needle-like 151 physical mechanisms occurring in 142 physics of 144-146 polymeric structures 148 PPV derivatives used as active materials in 152-154 prototypes 142 recent developments 168-171 single layer 144 structural control 148 working mechanism 145 leuco-emeraldine salt (LS) 260 Lewis acids 196. 230 liquid crystal devices 71 liquid crystal displays (LCDs) 168. 413 Langmuir films 381. 401 X-type 400-402 Y-type 400-402 Langmuir-Blodgett films 271. 355. 385. 384. 318. 411. 383 Langmuir trough 381. 383-385. 399-404. 321-322 lactate oxidase (LOD) 312-313. 387. 314.

55. 58. 134 luminance enhancement 371 luminance output 371 luminance-voltage characteristic 372 luminescence 101-103 basic principles 100 luminescence quenching 118 luminescence studies 99-140 luminescent organic compounds 367 luminous efficiency 369.2′-bithiophene-5. 376 magnetic disks 273 magnetic susceptibility of conducting polymers 56-58 magnetic susceptibility studies 23 magnetoconductance (MC) 45 in conducting polymers 50-54 maximum extinction coefficient 102 medical diagnostic biosensor application 297 MEH-PPV 151. 159. magnetoconductance versus field 51 metallic oriented-(CH)x 53 metallic polymers 13 metallic state in doped conducting polymers 39-49 metal oxide nanoparticles 345 methacrylate esters. 350-352. 59 metallic I-(CH)x.Index liquid crystalline polyimide.5′diyl (3MOT) 76 methyl methacrylate 204 methyl methacrylate-butyl methacrylate copolymer 121 methyl methacrylate-ethyl methacrylate copolymer 121 methyl tetrahydrofuran (MTHF) 115 microactivity-based device structure 374 M Mach-Zehnder (MZ) interferometer 87 magnesium 370 463 . 370 LUMO (lowest occupied molecular orbital) 144-145. 38-39. 230-231 schematic representation 231 lithium metal anode 243 lithium metal oxide cathode 233 lithium polymer electrolytes 218-239 lithium triflate 163 lithographic methods 188 contact mode 188 projection mode 188 proximity mode 188 lithography 286 Li4Ti5O12/LiPF6-EC-PC-PAN/LiMn2O4 cell 238 Li/TiS2 cell 222 LiX 218-219 lower critical solution temperature (LCST) 121. 18. PMMA copolymerised with 85 methacrylic acid 204 methacryloyl chloride 204 3-methyl-4′octyl-2. 347. 238 lithium-ion battery 217. 360 Meldrum’s acid 198 membranes 271-296 mercury lamp 188 mercury-rare gas (xenon) discharge lamp 188 metal/conducting polymer junctions 408 metal-insulator (M-I) transition 12 metal-insulator-semiconductor (MIS) diodes 406 metal-insulator transition 15. 232 lithium batteries 218-239 lithium battery 243-245 R&D projects 223 lithium-doped conducting polymer 243-245 lithium intercalation-deintercalation processes 232-234. change in lifetime during heating 135 liquid electrolytes 217. 354.

5-dimethoxy-pphenylene vinylene (MOPPV) More’s law 185 MOSFETS 410 Mott-Hubbard model 6 MRS see microresists for shorter wavelengths (MRS) multilayer resists (MLR) 208-209. 195 MOPPV see poly-(2.Handbook of Polymers in Electronics microactivity structure 371 microactuators 255-270. 121 naphthyl-substituted polymethacrylate (PNMA) 110 n-BCMU-PDA 75-76. 25 NADH 321-322 Nafion 240 nanocomposite polymer electrolytes 223 nanocomposites 342 benefits 343 metal nanoparticles 344 particle shape 343 preparation methods 344-346 nanocrystal probes 341 nanocrystals 341 nanoparticle components 341-365 nanoparticle photocurrent spectral response 354 nanoparticle properties 341 nanoparticles 342 preparation methods 344-346 size-dependence 344 nanoparticle semiconductor-polymer systems 353-357 nanotubes 255 nanowires 418 naphthalene 107. 379 molecular structure conformational changes 256 of heteroaromatic polymers 80 molecular weight effects on excimer formation 113 Monazoline process 193. 76 n-butoxycarbonylmethyl urethane) (nBCMU-PDA) 74 n-doping 242 near-field scanning optical microscopy (NSOM) 358-359 needle-like LED 151 negative bipolaron 11 negative deep-UV resists 201-202 examples 203 464 . 397 use of term 393 molecular interaction 99 molecular motion 99 molecular scale anisotropy 54 molecular scale transistors 367-368. 379 conducting polymers in 393-439 applications 394. 209 silicon-containing polymers 210 technology 209 muscles 255 N Naarman polyacetylene 14. 24. 423-424 applications 424 microbiosensors 276 microlithography development 189 dry development 189 exposure 188-189 processing 187-190 techniques 186 wet development 189 microresists for shorter wavelengths (MRS) 201 microscopic charge transport mechanism 54 miniaturisation 379 MIS field-effect transistors (MISFETs) 409 molecular devices based on conducting polymers 406-424 molecular diffusion 424 molecular electronics (ME) 368.

423 electrolytic expansion 263 thermoelectric power 63 PANI-AMPSA 48 conductivity versus temperature 48 PANI-CSA 55. 256. 72 materials characteristics 84 optical technology 69 organic electroluminescence 367. 232. 56. 314. 395. 274. 61 magnetoconductance 53 magnetoconductance versus field 54 O octadecanoic acid 381.Index negative electron-beam resists characteristics 206 formulae 207 negative magnetoresistance 59 negative polaron 10 negative polyimides 209-210 negative soliton 8 Neotronics 417 neutral soliton 8 nickel catalyst polymerisation 167 NIMA 381 n-methylpyrrolidone 398 N-methyl-2-pyrrolidinone (NMP) 257 NMP solution 266 non degenerate ground state 7. W versus temperature 59 oriented K-(CH)x. 397. 344. 257.4-oxadiazole 158. 402. 342. 159. 243 PANI 3. 82-84 non linear optical (NLO) properties 6998 non radiative energy transfer 121 non radiative resonance transfer 118 non radiative transition 109 ‘normal’ fluorescence 102 novolac resin 193 nuclear magnetic resonance (NMR) spectroscopy 8. 71 non linear optical (NLO) devices 69 non linear optical (NLO) materials 69 non linear optical (NLO) polymers 69 future targets for optical device applications 93-94 third-order 71-72. non linear 69-98 optical second-harmonic generation 386 optical signal processing 72 optical spectrometer 105 optical switching devices 71. 42. 159 oxidation 10 resistance 148 oxidative coupling method 398 P PAB/GOD 320 packaging materials 284 PAN 225. 38. W versus temperature 59 osmium-containing polymers 274 oxadiazole 158 1. 394. 369. 230. 37. 316. 9 non labelled PS 117 non linear optical (NLO) chromophores 69.3. 415 one-dimensional electronic system 5 1-methylnaphthalene 116 optical absorption edge 3 optical biosensors 314 optically detected magnetic resonance (ODMR) 10 optical properties. 227. 54. 243. 382 3-octadecanoylpyrrole (3ODOP) 402 3-octadecylpyrrole (3ODP) 402 Odour Mapper 417 odour sensors 414-417 one-dimensional chain 40 465 . 40. 370 organic molecules 393 oriented I-(CH)x. 227. 413.

273. 111 photobleaching 91 photochemical processes 105 photoconductors 273 photocurrent/dark current ratio 351 photocurrent measurement 348 photoelectron spectroscopy 406 photoexcitation 142. 421 photon absorption 143 photonic crystals 350 photonics 367 photons 119. 92. 40 phonons 20. 143 photoinduced absorption 10. 186. 207 PDABT 166 p-doping 242 PDTB 81 PEDOT 53. 21 Peierls-Hubbard model 6 Peierls instability 4. 371 photo-locking 208 photoluminescence (PL) 142-143 efficiency 166 quantum efficiency 143. magnetoconductance 53 Peierls distortion 6. 225. 56 PAV see poly(arylenevinylene) (PAV) PC see propylene carbonate (PC) PCHMT 165 PCHT 165 PCMS 206. 406 photooxidation 119 photophysical deactivation processes 100-104 photophysical processes 105. 398. 16. 145 spectra 372.10-perylenetetracarboxylic dianhydride (PTCDA) 285 P(ETMA-co-MMA) 206. 273. 54.9. 109. 143 photoisomerisation 256 photolithography 75. 367.4. 220 PEO-LiX 220. 188. 6 PEO see poly(ethylene oxide) (PEO) PEO-LiCF3SO3 224 PEO-LiClO4 219. 223. 243 membranes 218-219 pernigraniline salt (Pas) 260 3. 142. 394 Peierls model 5. 102. fluorescence spectra of 114 phenyloxysuccinimid 200 phonon freezing 21.Handbook of Polymers in Electronics W versus temperature 59 PANI-Nafion composite electrodes 320 PANI-PET 151 PANI-SiO2 344 PANI-TiO2 344 PANI-uricase electrode 313 parahexaphenyl (PHP) 161 Pariser-Parr-Pople model 6 parylene C (poly(chloro-p-xylene) 285 Pauli susceptibility 13. 367 characteristics 192 conventional 193 negative 194-197 one-component systems 194-195 positive 193-194 t-butyl carbonate (T-BOC) 199 two-component systems 196-197 466 . 344 normalised resistivity versus temperature 49 PEDOT-PF6. 24 phonon scattering 21 phosphorescence 100. 108 photophysical quenching 104 photopolyimide 210 photopolymerisation 398 photopolymers 185 photoresists 185. 310-311 phenyl 107 phenyl methacrylate. 207 PF6-doped PPy 38 phase and modulation fluorometry 105 phase separation 126-135 pH dependence of electrolytic expansion 262 pH effects 302. 14.

37. 397 polyacrylamide (PAAM) 240. 19. specific types photosynthesisers 398 photovoltaic properties 347 pH sensitivity 316 phthalocyanines 385 physical adsorption 306 physical vapour deposition (PVD) 276 physical vapour synthesis 345 π-bond 375 π-conjugated final structure 73 π-conjugated polymers 72 processible 76-82 π-electron bonding 342 π-electron conjugated polymers 71 π-electron conjugated structure 3 π-electron conjugation 79 π-electron delocalisation 142 π-electron hopping matrix element 41 π-electrons 5. 320 sensitivity curve 207 PNIPAM 122 PNMA see polymethacrylate (PNMA) PNVC 346 polarisation ratio 170 polarised electroluminescence 168-170 polaron-exciton levels 143 polaronic clusters 26 polarons 4. 396 energy levels and localised states 10 formation 9 instability 17 negative 10 polyacenaphthalene 115 polyacetylene 12. 40. 241-242 volume phase transition 134 polyacrylonitrile see PAN poly(3-alkoxycyanoterephthalylidene) 422 polyalkylfluorene 420 polyalkylthiophene (PAT) 38. 1164 structure 166. 225. 342. 197. 423. 203. 319. 227. 377. 37. 256. 14. 209. 72. 398 advantages over conventional polymers 278 gas parameters 281-282 general characteristics 277-278 history 277 power parameter 282 reactors 279-281 synthesis 278-282 plasma polymerisation/vapour deposition (PP/VD) 284 plasma polymers applications 283-290 characterisation 282-283 films 282-283 platelet reinforcement 343 PMAN see poly(o-methoxyaniline) (PMAN) PMMA 92. 207. 164. 9-12. 20. 167 synthetic procedures 167 trans conformation 165 polyamic acid 211 polyamide 6 342-343 poly-o-aminobenzoic acid 413 polyaniline (PANI) see PANI poly(aniline-co-ortho anisidine) 398 polyaniline film 265 anisotropy of electrolytic expansion in 266 contraction under strain 267 electrochemistry 259-260 expansion behaviour 259-260 expansion ratio 260-261 467 . 394. 422. 376 piezoelectric coefficient 379-380 piezoelectricity 386 Pioneer Corporation 369 plasma deposition technique 188 plasma etching 190 plasma polymerisation 276-282. 286. 256. 267. 6. 27. 255. 147. 255. 346.Index see also polimide-based photoresists. 243.

398 poly(3. 468 .6-dimethylphenylene oxide (PPO) 119. 398 polydiacetylene-polyacetylenepolydiacetylene triblock polymer chains 342 poly(9.4-ethylenedioxythiophene) (PEDOT) 49. 413 poly(ethoxyaniline) 403 poly(3. 403 poly(aromatic sulfones) 197 poly(arylenevinylene) (PAV) 72-74. 403. 405 poly(3-n-hexylthiophene) 408 polyimide 209-210. 219. 76. 169 polyfuran (PFu) 3 polyheptadiene 8. 164 poly(9-9. 397 polyheterocycles 243 poly(hexafluorobutyl-methacrylate) 204 poly(3-hexylthiophene) 400.4phenylene)-block-poly(2. 121 poly(dimethyltetrafluoropropylmethacrylate) 204 poly-(2.4-ethyelene dioxythiphene) 40 poly(ethylcyanoacrylate) 204 polyethylene (PE) 107.4hexadiyne-1. 262 electrolytic expansion 262-264 poly[2-methoxy-5-(2′-ethylhexyloxy)-pphenylene vinylene] 422 poly(2-methyl-1-pentene) 205 poly(methyl-isopropenyl-ketone) (PMIPK) 203 polymethyl methacrylate (PMMA) 107. electronics applications 367-391 polymer science 141 polymer spin coating process 380 polymer transistors 367 polymethacrylate (PNMA) fluorescence in different solvents 112 naphthyl-substituted 110 poly(o-methoxyaniline) (PMAN) 256. 395 polyconjugated chains 4.5-dimethoxy-p-phenylene vinylene (MOPPV) 72-74 poly-(2. 261.5-benzoxazole)-blockpoly(benzobisthiazole-2-hydroxy-1. 273 formation 211 polyimide-based photoresists 209-210 characteristics 210 examples 212 polyindole 395. 37 polycyclohexyl methacrylate 133 poly(3-cyclohexylthiophene) 408 polydiacetylene (PDA) 72. 221-224 see also PEO polyethylenimine (PEI) 289 polyfluorene 162-164.5-benzoxazole) 342 poly(2.9-di(ethylhexyl)fluorene (PDF2/6) 163.6-diol] (PTS-PDA) 72 polycarbazole (PCz) 3. 398 poly(2. 422 poly-2.dihexylfluorene) 162.Handbook of Polymers in Electronics polyaniline insulated gate field-effect transistors (PANI-IGFETs) 410 poly(o-anisidine) 402. 159 polyethylene glycol/polyurethane copolymer 275 polyethyleneimine-H2SO4 240 poly(ethylene oxide) (PEO) 218. 413 poly(N-isopropylacrylamide) (PNIPAM) 121 poly-L-lysine 290 polymer chain 10 conformation effect of 110-118 polymer compatibility 121 polymer deposition technologies 379-387 polymer electroluminescence 368-374 polymers.5benzoxazole) 342 polybenzimidazole (PBI) 240 poly[bis(p-toluenesulfonate) of 2.6-dimethyl-p-phenylene oxide) 120 poly(3-dodecylthiophene) 76 polyemeraldine base (PEB) 318.

81 poly(phenylene ethynylenes) 162 polyphenylenes 148-164 poly(phenylene vinylene) 11 poly(phenyl methacrylate) (PPMA) conformation change of 113 fluorescence spectra of 113. 160. 20. 398 poly(o-phenylenediamine) 305 polyphenol 305 polyphenylene derivatives 160-161 polyphenylenediyl-pyridinediyl (PPPY) 80. 74 poly(thiophene-2. 126. 420 time-resolved fluorescence spectra for 116 time-resolved fluorescence spectra of 116 polyvinylcarbazole (PVCZ)/urease electrodes 316 polyvinylchloride (PVC) 319 poly(vinylcinnamate) 194 polyvinylidene difluoride (PVdF) 379-380 polyvinylidene fluoride (PVdF) 225 polyvinylnaphthalene (PVN) 107. 404. 164168. degradation 205 polysulfur nitride 398 polythiazyl (SN)x 3 polythienylene vinylene (PTV) 37. 306.5-diyl) 81 polythiophenediyl-bipyridinediyl (PTBPY) 80-82 polythiophenediyl-pyridinediyl (PTPY) 80-82 polythiophene (PT) 3. 116. 76. 274.5-diyl) 81 polypyrrole see PPy polysiloxanes 284 poly(sodium 4-styrenesulfonate) 387 polystyrene (PS) 107. 395.6-dimethylphenylene 469 . example 211 positive polaron 10 positive polyimide resists 210 positive soliton 8 post baking 190 potassium tert-butoxide 149 potentiometric biosensors 301. 159. 402. 37. 119 fluorescence 120 lifetime data 125. 126 lifetime parameters 120 polystyrene sulfonated acid (PSSA) 159 polysulfone. 342-345. 395. 159 copolymerised with methacrylate esters 85 poly(3-methylthiophene) 40. 38. 72. 133 polyvinylphenol (MRS) 203 poly(4-vinylpyridine) 274 polyvinylpyrrolidone (PVP) 240. 115 poly(p-phenylene) (PPP) 3. 114. 285. 398. 422 poly(p-phenylenevinylene) see PPV polypropylene (PP) 107 poly(pyridine-2. 115. 346 poly-p-xylene 286 Poole-Frenkel effect 407 POPT 165 portable conformable masking (PCM) 208 positive bipolaron 11 positive deep-UV photoresists one-component systems 197 two-component systems 198 positive electron-beam resists 203-205 positive MR 61 positive photopolyimide resists. 406 poly-4-vinylbiphenyl 107 polyvinylcarbazole (PVCZ) 107. 206 polyparaphenylene (PPP) 37. 407 polynaphthyl methacrylate in chloroform 111 poly(olefin sulfones) 205. 377. 315-317 power law behaviour of conductivity 58 p(PMMA-OM-MAN) 197 PPO see poly-2. 397. 394.121.

402. 422 cis double bonds 151 derivatives used as active materials in LED 152-154 electroluminescence spectrum 150 soluble copolymers based on 151 structure 149 sulfuric acid doped 45 synthetic procedure 149 PPV-AsF5 42 PPV-based ladder copolymers 423 PPV-based polymers 360 PPV-H2SO4 42. 53. 58 heat capacity versus temperature 57 magnetoresistance versus resistivity ratio 62 normalised resistivity versus temperature 47 S(T) 55 W versus temperature 59. 417. 317. 420. 38. 305. 274. 267. 9. 54. 17. 72. 324. 423 cathode 243 doped with PF6 (PPy-PF6) 46 films 307 heat capacity versus temperature 57 PPy-Fe2O3 344 PPy-ferrocene carboxylic acid based cholesterol biosensor 323 PPy-PF6 56. 81. 408. 141. 38. 346. 244. 207 PVN see polyvinylnaphthalene (PVN) PVP see polyvinylpyrrolidone (PVP) p-xylene polymer 286 pyrene 107. 318. 268. 10. 60 PPy-polyvinyl sulfonate films 312 PPy-PVS/LDH electrodes 322 PPy-SiO2 344 PPy-p-toluenesulfonate (TSO) 57 PPy-ZrO2 344 pre-exponential function 105 propylene carbonate (PC) 222 proton membranes. 320. 121 emission intensity 122 pyrene-labelled PS 117 pyridine 158 pyridine rings 81 pyroelectric coefficient 379-380 pyroelectricity 386 pyrrole/3ODOP film 402 pyrrole 398 pyruvate biosensor. conductivity 241 proton polymer electrolytes 239-242 PSTF 82 molecular structure 83 waveguide 84 PT see polythiophene (PT) PTBPY see polythiophenediylbipyridinediyl (PTBPY) PtO 343-344 PTOPT 165 PTPY see polythiophenediyl-pyridinediyl (PTPY) PTV see polythienylene vinylene (PTV) pulse fluorometry 105 PVCZ see polyvinylcarbazole (PVCZ) PVMS 206.Handbook of Polymers in Electronics oxide (PPO) PPP see polyparaphenylene (PPP) PPPY see polyphenylenediyl-pyridinediyl (PPPY) PPV 3. 344. 406. 397. 326. 53. 60 magnetoconductance 52 magnetoconductance versus field 51 resistivity versus temperature 46 PPy 3. 37. 42. 413. 342. 74. 40. 316. 345. 394. 40. 148-160. 342. 418. 37. calibration graph 314 Q q-1D 4 conduction path 21 electronic systems 39 fractals model 22 470 . 347. 398. 395.

418 scanning transmission microscopy (STM) 404 471 . 104. 110. 104. 94. 118 quinine sulfate 106 quinone-hydroquinone reaction 317 quinoxaline 158 R radiation 99 frequency 99 intensity 99 types 188 radiationless processes 103 radiative recombination 146 Raman spectroscopy 227 random dimmer model (RDM) 26 rate constant 101. 130 reactive ion etching (RIE) 89. 92. 405. 23 Mott’s law 22 percolation model 27 transport 24 variable range hopping model 19 quantum lattice fluctuations 4 quantum yield 105-106 definition 105-106 quartz crystal microbalances (QCM) 289 quasi-one-dimensional material see q-1D quasi-one-dimensional (q-1D) material 4 quasi-phase-matching (QPM) polymer waveguide 90 technique 88 waveguide fabrication method 89 quenching processes 103. temperature dependence 43. 192 removal (stripping) 190 requirements 190-192 sensitivity 191 solubility 191 special 208-211 see also multilayer resists (MLR) reversible electrochemical actuators 424 rhodamine B 106 RIE see reactive ion etching (RIE) rocking chair battery 230-231 S salicylic acid (SA) 241 sample preparation 257 sandwich configuration 347 SBAC polymer 76-78 synthetic scheme 78 transition dipole moment between 1Bu and 2Ag excited states 77 wavelength dependence 78 scanning electron microscopy (SEM) 23. 192 positive 189. 108. 103. 115.metallic chain 22 models 22. 57 resists adhesion 191 coating process 188 contrast 191 etching resistance 191 films 286 materials 193-210 negative 189. 190 reactors for plasma polymerisation 279 recombination of electron-hole pairs 371 radiative 146 recombination process 347-348 red-green-blue (RGB) emission 161 redox behaviour 259 redox current 257 redox potential 302 redox reaction 304 refractive index grating fabrication 90 regioregularity 167 resistivity. 45 resistivity ratio 12.

380 sputter etching 190 sputtering 273 stability 141. 38.2O2 cell 237 SnO2/LiNi0. multilayer resists 210 silicon monoxide 284 silicon transistor 379 single crystals 380 single layer LED 144 single photon fluorometer 105 singlet excitation. 346.2 O2 battery 237 SnO2/LiNi0. 11.2O2 electrodic couple 236 solid electrolyte interface (SEI) 233 solid-state polymer laser diodes 350 soliton band 18 solitons 6-9.Handbook of Polymers in Electronics scattering rate 41 Schottky devices 406-408 Schottky diode 357 Schrieffer-Heeger model 15 second-harmonic generation (SHG) 88. 91 efficiency and laser power 90 second-order NLO polymers 84-87 self-assembled films 271 self-assembly monolayers 404 self-phase modulation (SPM) 83 semiconducting polymers 341-365 semiconducting state 6 semiconductive films 285 semiconductor nanoparticles 345 semiconductors 4. 396 energy levels and localised level occupations 8 formation 8 interchain transport 20 physical properties 8 special resists 208-211 specific heat of conducting polymers 5658 spectral bandwidths 373 spectral sharpening 371 spectral studies 105 spectroscopic methods 406 spin coating 151.8 Co0. 355 Smoluchowski equation 118 SnO2/LiClO4-EC-DMC-PAN/LiNi0. on Si 187 SiO2 fibre 84 6FPBO 354. 271. 276277.8 Co0. 19. 148 steady-rate fluorescence emission spectrum for iPS gel 132 Stern-Volmer equation 104 Stokes law 99 structure modulation 157 sub-gap optical absorption bands 143 substituted benzylidene aniline with chloride polymer see SBAC substituted polyparaphenylene 160 sulfonium precursor polymer 149 sulfuric acid doped PPV 45 supercapacitor research and development 217 surface plasmon resonance (SPR) 273. processes occurring after 109 singlet exciton 143 singlet ground state 100 SiO2. 289 472 . 393 sensing devices 297 sequential monolayer tranfer process 384 sequential transfer process 383 serially-grafted polymer waveguides 8890 sexithienyl based FETs 410 σ bond 375 signal processing by optical technology 69 signal processing function 69-70 signal transmission function 69-70 silicon 375 SiO2 on 187 silicon chip 393 silicon-containing polymers. 16. 394. 273. 188.8Co0.

7. plasma-polymerised 285 thiophene rings 81 third-harmonic generation (THG) 74. 39. 286 tetraethylorthosilicate (TEOS) 418 tetrahydrofuran-ether 111 tetrahydrofuran (THF) 113. 83 third-order NLO polymers 71-84 research background 71-72 waveguides 82-84 three-dimensional band calculations 17 three-dimensional coupling 17 three-fold helical conformation 132 tight-binding model 17 time-correlated single-photon counting studies 105 time-dependent studies 105 time-of-flight (TOF) measurements 397 time-resolved fluorescence spectra iPS/BA gel 130 iPS gel 131 PVCZ 116 time-response of electrolytic expansion 265 TiO2 343 TiO2-conjugated polymer composites 348-353 TiS2 221 toluene sulfonic acid 264 trans-cis-trans isomerisation 91 transducers 299. 271.N-di-pmethoxyphenyl-amine)9. 148.2′.7′-tetrakis(N. temperature dependence 55 thermoelectric power (S(T)) of conducting polymers 55 thermo-optical polymer devices 71 thermotropic liquid-crystallime polyimide 135 thermotropic liquid-crystalline (LC) polyimide (P-11TPE) 134 2. 91. 47. 17. 301. 201 t-butyl carbonate (T-BOC) photoresists 199 Teflon 398 temperature coefficient of resistance (TCR) 13. 55 terephthaldicarboxaldehydes 148 terephthalic aldehyde 77 tetracyanoquinodimethane (TCNQ) 274. 48.9′spirobifluorine 353 tetramethylammonium hydroxide 73 tetramethyltin (TMT) 285 tetraphenyl diaminobiphenyl (TPD) 158 TGA 397 thermal ageing test 86 thermal property measurements 57 thermoelectric power.surface polarity 148 Su-Schrieffer-Heeger (SSH) model 6. 49. 77. 284 applications 273 new materials 271 thiophene.5-thienylene bis(methylene-dimethylsulfonium chloride) 72-73 thin films 71-74. 41-43. 44 taste-sensing field-effect transistor (TSFET) 415 taste sensors 414-415 T-BOC-PHS 200 decomposition in acid medium 200 T-BOC polymers 200 t-butyl acrylate 200. 38. 142 sweep voltametry 227. 14. 120 2. 76. 230 T T1/2 law 14. 313 transistors molecular-scale 367-368 polymer 367 transistor-transistor logic (TTL) 87 transmission electron microscopy (TEM) 23 473 .

8. 52. minimum size versus year 185 VLSI electronic circuits 273 VLSI technology 185. 10. 74 X-ray lithography 186. 39.2′-bipyridyl ruthenium) complex 398 4. 61-62 Z Ziegler-Natta catalyst 397 ZnSe 353 Z-type deposition 401-402 474 . 212. 17. 11. 276-277 voltage profile 233 volume phase transition of PAAM 134 W Wannier exciton 143 water-soluble polymers 387 waveguide grating 92 diffraction efficiency of 91 waveguides 69. 25. excimer photophysics for 133 two-photon resonance 86 very large scale integration see VLSI vibrational relaxation (VR) 100.Handbook of Polymers in Electronics trans-polyacetylene (PAc) 3. 23. 13.4′. 71 third-order NLO polymer 82-84 weak localisation (WL) 50. 143 variable-range hopping (VRH) model 19. 399-404 ultraviolet photoelectron spectroscopy (UPS) 11. 7. 111 tris (2. 283 X-ray resists 206-208 V vacuum-deposited SBAC polymer 77 valence band 4. 19. 102 vinyl polymers with substituents R and R′ 106-107 VLSI. 395 transport properties of polymers 12-14 factors influencing 14-18 transport property measurements 39 triazole 158 TRIDSB 157 trifluoromethane sulfonic acid 199 triphenyl sulfonium triflate 199 triplet exciton 144 triplet state 101. 22. 206 X-ray photoelectron spectroscopy (XPS) 282. 54 Wessling method 149 Wilhelmy plate 381 Wittig condensation 148 U ultrathin films 286. 159 unoriented I-(CH)x.4′′-tris(1-naphthyl)-(N-phenylamino)triphenylamine 169 tunable photonic crystals (TPCs) 350 two-phase system. W versus temperature 59 unsubstituted PPV 158 unsubstituted thiophenes 164 urea biosensor 320 X X-ray diffraction (XRD) 23. 394.

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