Organic Electronics Materials, Manufacturing and Applications Edited by Hagen Klauk WILEY- VCH WILEY-VCH Verlag GmbH & Co. KGaA
The Editor Dr. Hagen Klauk Max Planck Institute for Solid State Research Heisenbergstr. 1 70569 Stuttgart Germany All books published by Wiley-VCH are carefully produced. Nevertheless, authors, editors, and publisher do not Warrant the information contained in these books, including this book, to be free of errors. Readers are advised to keep in mind that Statements, data, illustrations, procedural details or other items may inadvertently be inaccurate. Library of Congress Card No.: applied for British Library Cataloguing-in-Publication Data A catalogue record for this book is available from the British Library. Bibliographie information published by Die Deutsche Bibliothek Die Deutsche Bibliothek lists this pubhcation in the Deutsche Nationalbibliografie; detailed bibliographic data is available in the Internet at <http://dnb.ddb.de>. 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim All rights reserved (including those of translation into other languages). No part of this book may be reproduced in any form - by photoprinting, microfilm, or any other means - nor transmitted or translated into a machine language without written permission from the publishers. Registered names, trademarks, etc. used in this book, even when not speeifieally marked as such, are not to be considered unprotected by law. Typesetting Asco Typesetter, Hong Kong Printing Strauss GmbH, Mörlenbach Binding Schärfer GmbH, Grünstadt Cover Design Grafik-Design Schulz, Fußgönheim Printed in the Federal Republic of Germany Printed on aeid-free paper ISBN-13 978-3-527-31264-1 ISBN-10 3-527-31264-1
Contents I 1 1.1 1.2 1.2.1 1.2.2 1.2.3 1.2.4 1.3 1.3.1 1.3.2 1.4 1.5 1.6 1.6.1 1.6.2 1.6.3 1.6.4 1.6.5 1.7 II 2 2.1 2.2 2.2.1 2.2.2 2.2.3 2.2.4 2.2.5 2.3 2.4 2.5 2.6 Preface Author List Organic Transistors Gilles Horowitz Overview of the Organic Thin-film Transistor Are Organic ``Semiconductors'' Real Semiconductors? Thin-film Transistor Architecture Operating Mode Thickness of the Channel Contact Resistance Contact Resistance Extraction Origin of Contact Resistance Charge Transport Fabrication Techniques The Materials Polymers Small Molecules n-type Semiconductors Single Crystals Insulators Concluding Remarks Acknowledgements Advanced Materials for Organic Electronics High-performance Pentacene Transistors Tommie Kelley Routes to Performance Improvement Purification Device Evolution Structural Perfection Device Architecture Interfacial Control Structure--Property Relationships Continuing Reports of High Mobilities Performance in Practice The Future of High-performance Organic Transistors XIII XV 1 3 3 4 4 7 8 10 15 15 19 20 21 23 23 24 25 26 27 28 29 29 33 35 35 38 38 39 39 41 45 48 51 52 53
3 3.1 3.2 3.3 3.4 3.5 3.6 3.7 4 4.1 4.2 4.3 4.4 4.4.1 4.4.2 4.4.3 4.4.4 4.4.5 4.5 4.6 5 5.1 5.2 5.2.1 5.2.2 5.3 5.3.1 5.3.2 5.3.3 5.3.4 5.4 5.4.1 5.4.2 5.4.2.1 Engineered Pentacenes John E. Anthony Reversible Functionalization 2,3,9,10-Tetrasubstituted and 2,3-Disubstituted Pentacenes: End-substituted Derivatives Peri-functionalized Pentacene Pentacene Functionalized at Both peri and End Positions Heteropentacenes Conclusion Organic Semiconductors Based on Polythiophene and Indolo[3,2-b]carbazole Beng S. Ong, Yiliang Wu, and Yuning Li Issues and Challenges Structural Considerations Polythiophene Semiconductors High-performance Polythiophene Design Polydialkylterthiophenes Polydialkylquaterthiophenes Polythiophene Nanoparticles Inkjet Patterned TFT Arrays Indocarbazole Designs Summary and Prospects Acknowledgements Electrical and Environmental Stability of Polymer Thin-film Transistors Alberto Salleo and Michael L. Chabinyc Charge Trapping in TFTs General Considerations Bias Stress in Organic Transistors Bias Stress in Polyfluorene and Polythiophene TFTs Reversible Bias Stress Long-lived Bias Stress Dependence of Bias Stress on Operating Conditions; Lifetime Predictions A Microscopic Theory of Bias Stress Chemical Effects on Stability---Defects and Impurities Defects in Molecular Structure Defects from Synthesis 54 58 58 59 60 63 68 69 72 72 75 75 76 79 80 81 82 87 90 94 95 103 105 105 108 108 109 109 111 112 113 115 116 118 119 119 120 120
5.4.2.2 Photo-induced Defects 121 5.4.3.1 Thermochemical Analysis 123 5.4.3.2 Oxygen 5.4.3.3 Water 5.4.3.4 Organic Solvents 5.4.3.5 Inorganic Impurities 5.4.3 Impurities 5.4.4 Studies of TFT Lifetime 128 5.5 Conclusion 6 Gate Dielectrics 132 Marcus Halik 6.1 6.2 The Impact of Gate Dielectrics on the Electrical Functionality of 133 Organic TFTs 6.3 Insulating Materials---An Overview 135 6.3.1 Inorganic Gate Dielectrics 136 6.3.2 Polymer Gate Dielectrics 137 6.3.3 Self-Assembled Monolayer Gate Dielectrics 138 6.3.4 Multi-layer and Multi-component Gate Dielectrics 139 6.3.5 Multifunctional Dielectrics 140 6.4 Application-related Aspects of Dielectrics 140 6.4.1 Poly-4-vinylphenol Dielectrics 141 6.4.2 The Self-assembled Monolayer Approach 153 7 Advanced Flexible Polymeric Substrates 163 William A. MacDonald 7.1 7.2 Polyester Substrates 163 7.3 Properties of Base Substrates 165 7.3.1 Optical Properties 165 7.3.2 Birefringence 166 7.3.3 Thermal Properties 166 7.3.4 Solvent Resistance 167 7.3.5 Surface Quality 170 7.3.6 Mechanical Properties 172 7.3.7 Summary of Key Properties of Base Substrates 173 7.4 Multilayer Structures 174 7.5 Film in Application 177 178 178 124 126 127 127 123 129 129 129 132 161 163
III Manufacturing for Organic Electronics 181 8 Reel-to-reel Vacuum Metallization 183 Roland Treutlein, Martin Bergsmann, and Carl J. Stonley 8.1 Reel-to-reel Vacuum Metallization 183 8.1.1 The Metallization Process 184 8.1.1.1 Evaporation Sources 184 8.1.1.2 Pretreatment and Cleaning of the Web Substrate 186 8.1.1.3 PVD Process Flow 186 8.1.1.4 Typical Process Times, Rates, and Quantities 189 8.1.1.5 Transfer Metallization 190 8.1.1.6 Pattern-evaporated Layers 191 8.1.2 Properties of the Evaporated Layer 191 8.1.2.1 Structure 191 8.1.2.2 Layer Thickness (Conductivity) 192 8.1.2.3 Barrier 195 8.1.2.4 Light Barrier 197 8.1.3 Environmental Benefits of Vacuum Evaporated Layers 198 8.1.4 Applications of Metallized Films 199 8.1.4.1 Barrier Packaging 199 8.1.4.2 Decorative Applications 199 8.1.4.3 Functional Layers 199 8.1.4.4 Polymer Electronic Substrates 200 8.1.5 Market Analysis 201 202 9 Organic Vapor Phase Deposition 203 Michael Heuken and Nico Meyer 9.1 203 9.1.1 The Principle of OVPD 203 9.1.2 Close Coupled Showerhead Technology 204 9.2 Deposition of Organic Thin Films 207 9.2.1 Process Control in OVPD 207 9.2.2 Co-deposition and Doping in OVPD 211 9.2.3 Controlled Morphology and Layer Interfaces in OVPD 213 9.3 Electronic Devices by OVPD 215 9.3.1 OLEDs Made by OVPD 215 9.3.2 Organic Photovoltaics by OVPD 220 9.3.3 Organic Thin-film Transistors by OVPD 221 9.4 Full-color OLED Displays 222 9.4.1 Micropatterning by use of Shadow Masks 222 9.4.2 Mask-less Processes 224 9.5 Material Properties of Organic Molecules for Use in OVPD 225
9.6 10 10.1 10.2 10.3 10.3.1 10.3.2 10.4 10.4.1 10.5 10.5.1 Summary Acknowledgment Thermal Imaging and Micro-contact Printing Hee Hyun Lee, John Rogers, and Graciela Blanchet Building Blocks Printing and Patterning Techniques Thermal Imaging Printed Devices: From TFTs to Large-area Backplanes Printable Materials Polyaniline Nanotube Composites: A High-resolution Printable Conductor Micro-contact Printing Contact Printing with High-resolution Stamps 10.5.1.1 High-resolution Stamps 10.5.2 10.5.3 10.6 10.6.1 10.6.2 10.6.3 10.7 11 11.1 11.2 11.2.1 11.2.2 11.3 11.3.1 11.3.2 Micro-contact Printing Nanotransfer Printing Large Area Stamps, Molds, and Photomasks for Soft Lithography Micro-contact Printing: A Path to Reel-to-reel Electronics Inexpensive Approaches to Large-area Printing Registration Using the Lock-and-key Mechanism in Soft Imprinting Conclusions Thin-film Transistor Fabrication by Digital Lithography William S. Wong, Jürgen H. Daniel, Michael L. Chabinyc, Ana Claudia Arias, Steven E. Ready, and René Lujan Jet-printed Patterning for Thin-film Transistor Processing Jet-printed Phase-change Etch Masks Digital Lithography Digital Lithography for TFT Device Fabrication Thin-film Transistor Device Structures 11.3.2.1 Amorphous Silicon TFTs 11.3.2.2 Polymeric TFTs by Digital Lithography 11.3.3 Thin-film Transistor Device Characteristics 11.3.3.1 a-si:h TFTs 11.3.3.2 Printed Polymeric TFTs 11.4 11.4.1 11.4.2 TFTs on Flexible Substrates TFT Pixel Design Considerations 226 229 229 233 233 233 235 235 236 240 240 245 245 246 247 251 259 259 259 264 266 268 265 271 271 272 272 273 276 276 277 277 279 282 282 284 285 285 285
11.4.3 11.5 11.6 12 12.1 12.2 12.2.1 12.2.2 12.2.3 12.2.4 12.2.5 12.2.6 12.2.7 12.3 12.3.1 12.3.2 12.3.3 12.4 12.5 IV 13 13.1 13.2 13.2.1 13.2.2 13.2.3 13.3 13.3.1 13.3.2 13.3.3 13.3.4 Digital Lithography for Flexible Backplanes Display Applications with Print-patterned Backplanes Conclusions Manufacturing of Organic Transistor Circuits by Solution-based Printing Henning Sirringhaus, Christoph W. Sele, Timothy von Werne, and Catherine Ramsdale to Printed Organic Thin Film Transistors Overview of Printing-based Manufacturing Approaches for OTFTs Screen Printing Offset Printing Gravure Printing Flexography Inkjet Printing Laser-based Dry-printing Techniques Other Nonlithographic Manufacturing Approaches High-resolution, Self-aligned Inkjet Printing Self-aligned Printing by Selective Surface Treatment Self-aligned Printing by Surface Segregation Self-aligned Printing by Autophobing Performance and Reliability of Solution-processed OTFTs for Applications in Flexible Displays Conclusions Devices, Applications, and Products From Transistors to Large-scale Integrated Circuits Gerwin H. Gelinck, Erik van Veenendaal, Eduard J. Meijer, Eugenio Cantatore, H. Edzer A. Huitema, Pieter van Lieshout, Fred J. Touwslager, Alwin W. Marsman, and Dago M. de Leeuw Discrete Devices Basic Device Operation of Organic Transistor Current--Voltage Characteristics Capacitance--Voltage Characteristics Fabrication and Characterization of Integrated Circuits Fabrication Modeling Analysis of Inverters Analysis of Integrated Circuits 287 290 291 291 291 294 294 297 298 299 300 300 301 302 302 304 305 307 308 314 318 319 319 323 325 325 326 326 327 328 330 331 333 336 340 342
14 14.1 14.1.1 14.2 14.3 14.3.1 14.3.2 14.4 14.5 14.6 14.7 14.8 14.8.1 14.8.2 14.8.3 15 15.1 15.2 15.3 15.4 15.5 15.6 15.7 15.8 15.9 15.10 15.11 15.12 15.13 15.14 15.15 15.16 15.17 15.18 15.19 Roll-up Active-matrix Displays H. Edzer A. Huitema, Gerwin H. Gelinck, Erik van Veenendaal, Fred J. Touwslager, and Pieter J. G. van Lieshout Non-rigid Display Research and Development Overview Rollable Active-matrix Backplane Technology Roll-up Active-matrix Backplane Design Field-effect Mobility Effects Leakage Current Effects The Electronic Ink Film Roll-up Display Integration Functional Active-matrix Roll-up Displays Roll-up Display Device Concepts Towards a System-on-plastic: Driver Integration Row Driver Integration Stand-alone Shift Registers Integrated Shift Registers Acknowledgment Active-matrix Light-emitting Displays Shelby F. Nelson and Lisong Zhou OLED Pixel Differences from LCDs Complex Pixel Design Practical Design AIM--SPICE Simulation of Pentacene TFT-driven OLEDs Fabrication Process Device Passivation PVA and Parylene Pentacene TFT Uniformity Stability Integration of TFTs and OLEDs Flexible OLED Display Substrate Selection and Mounting Thermal Dimensional Stability Surface Quality Chemical Resistance Fabrication Process Display Results Conclusion 342 344 344 345 346 349 351 353 354 355 355 358 358 358 360 362 364 364 367 367 369 369 370 372 375 376 380 381 383 384 386 387 387 388 389 390 390 391 392
16 Large-area Detectors and Sensors 395 Takao Someya and Takayasu Sakurai 16.1 16.2 16.3 16.4 16.5 16.6 16.7 16.8 16.9 16.10 17 17.1 17.2 17.3 17.4 17.5 Large-area Pressure Sensors Organic Transistor-based Integrated Circuits Bending Experiments of Organic Transistors High-temperature Operation of Organic Transistors Sheet Image Scanners Three-dimensional Integrated Circuits Future Prospects of Large-area Electronics Remaining Issues Conclusions Organic Semiconductor-based Chemical Sensors Howard E. Katz and Jia Huang Background Inorganic and Nanostrctured Semiconductor Sensors Sensitive Organic Field-effect Transistors Mechanistic Rationale Conclusion Index 395 396 398 400 401 402 405 407 407 408 409 409 411 411 412 414 416 418 419 422