Springer Series in MATERIALS SCIENCE 61 Springer-Verlag Berlin Heidelberg GmbH ONLINE LlBRARY Physics and Astronomy springeronline.com Springer Series in MATERIALS SCIENCE Editors: R. Hull R. M. Osgood, Jr. J. Parisi H. Warlimont The Springer Series in Materials Science covers the complete spectrum of materials physics, including fundamental principles, physical properties, materials theory and design. Recognizing the increasing importance of materials seience in future device technologies, the book titles in this series re fleet the state-of-the-art in understanding and controlling the structure and properties of all important classes of materials. 61 Fatigue in Ferroelectric Ceramics 67 Nondestructive and Related Issues Materials Characterization By D.C. Lupascu With Applications to Aerospace Materials Editors: N.G.H. Meyendorf, P.B. Nagy, 62 Epitaxy and S.1. Rokhlin Physical Foundation and Technical Implementation 68 Diffraction Analysis By M.A. Herman, W. Richter, and H. Sitter of the Microstructure of Materials Editors: E.J. Mittemeijer and P. Scardi 63 Fundamentals of Ion Irradiation ofPolymers 69 Chemical-Mechanical Planarization ByD. Fink of Semiconductor Materials Editor: M.R. Oliver 64 Morphology Control of Materials and Nanoparticles 70 Isotope Effect Applications in Solids Advanced Materials Processing By G.V. Plekhanov and Characterization Editors: Y. Waseda and A. Muramatsu 71 Dissipative Phenomena in Condensed Matter 65 Transport Processes Some Applications in Ion Irradiated Polymers By S. Dattagupta and S. Puri ByD. Fink 72 Predictive Simulation 66 Multiphased Ceramic Materials of Semiconductor Processing Processing and Potential Status and Challenges Editors: W.-H. Iuan and J.-K. Guo Editors: J. Dabrowski and E.R. Weber Series homepage - springer.de Volumes 10-60 are listed at the end of the book. Doru C. Lupascu Fatigue in Ferroeleetrie Ceramies and Related Issues With 80 Figures Springer Dr. Doru C. Lupascu Technische Universität Darmstadt Fachbereich Materialwissenschaften Nichtmetallisch-Anorganische Werkstoffe Petersenstrasse 23 64287 Darmstadt, Germany E-mail: [email protected] Se ries Editors: Professor Robert Hull Professor Jürgen Paris i University of Virginia Universität Oldenburg, Fachbereich Physik Dept. of Materials Seience and Engineering Abt. Energie-und Halbleiterforschung Thornton Hall Carl-von-Ossietzky-Strasse 9-11 Charlottesville, VA 22903-2442, USA 26129 Oldenburg, Germany Professor R. M. Osgood, Jr. Professor Hans Warlimont Microelectronies Seien ce Laboratory Institut für Festkörper- Department of Electrieal Engineering und Werkstofforschung, Columbia University HeImholtzstrasse 20 Seeley W. Mudd Building 01069 Dresden, Germany New York, NY 10027, USA ISSN 0933-033X ISBN 978-3-642-07301-4 ISBN 978-3-662-07189-2 (eBook) DOI 10.1007/978-3-662-07189-2 Cataloging-in-Publication Data applied for. 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Violations are liable for prosecution under the German Copyright Law. springeronline.com © Springer-Verlag Berlin Heidelberg 2004 Originally published by Springer-Verlag Berlin Heidelberg New York in 2004 Softcover reprint of the hardcover 1st edition 2004 The use of general descriptive names, registered names, trademarks, etc. in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use. Typesetting by the author Cover concept: eStudio Calamar Steinen Cover production: design & production GmbH, Heidelberg Printed on acid-free paper 57!3141!tr 543210 To Kathrin, my parents, and my brother Preface Ferroelectric devices are nowadays widely found in advanced technology as weIl as everyday household machinery. The broad range of physical properties in this class of materials has aIlowed for the evolution of devices ranging from piezoelectric components and optical devices to ferroelectric non-volatile memories in microelectronics. Examples extend from simple gas igniters, sonic and ultrasonic sensors and actuators to the more advanced ultrasonic motors, high precision positioning devices, optical switches and recently permanent memories for computer applications. Many more applications are anticipated. Particularly the fact that many parts are at the edge of becoming large numbered consumer products necessitates a much higher reliability of the devices. Two aspects are relevant with respect to this, an adequate device design to ensure a minimum loading of the ferroelectric material on the one hand, and optimized material properties for high reliability at maximum performance on the other. Unfortunately, ferroelectric materials are mostly brittle both as single crystals as weIl as polycrystalline material, and in the worst case even water soluble crystals. Particularly tensile mechanicalloading will often lead to an immediate failure of the device. On longer terms, cyclic loading will deteriorate the performance of the material. Multiple loading will either lead to cyclic crack growth or the modification of the material properties at the mesoscopic and microscopic level. During the last fifty years of material development it has become clear that effects on a wide range of time and size scales down to the atomic level are relevant for the properties of ferroelectrics. In these same ranges of times and sizes the sources of fatigue have to be identified. The present text is an attempt to assign the fatigue phenomenon in bulk ferroelectric ceramics to its microscopic, mesoscopic, and macroscopic sources. Darmstadt, October 2003 Doru Constantin Lupascu Acknow ledgement The largest difficulty in writing a book resides in an appropriate appreciation of the work of all those who have contributed to its successful completion. I would like to express my gratitude to all my colleagues and friends who have provided insight, generosity, numerous work hours, and plenty of joy during the last years. This book is the outcome of all this collaborate effort. First of all, I want to express my gratitude to Jürgen Rödel for his confi dence in my abilities and the continuous intellectual, financial, and personal support which have entered this and many other projects throughout the last years. Next, I am very grateful to Jürgen Nuffer, Cyril Verdier, and Markus Christman, who were directly involved in the fatigue studies and achieved many of the experimental results presented in this book in long laboratory hours. Furthermore, I would like to express my thankfulness to Sergio Louis dos Santos e Lucato and Alain Kounga, who have successfully worked on so many aspects of fracture of ferroelectrics. Achim Neubrand has been my brilliant office mate. The entire team of Nichtmetallisch-Anorganische Werkstoffe provided an ongoing pleasure in the daily work. Emil Aulbach, Markus Bürgers, Astrid Dietrich, Matthias Diemer, Jens Eichler, Susan Galal-Yousef, Roswitha Geier, Herbert Hebermehl, Daniel Hoffmann, Mark Hoffmann, Ralf Jedamzik, Jo hannes Kanters, Patricie Merkert, Thomas Ostrowski, Siegfried Skirl, Mar tin Stech, Ulrich Stiefel, Thomas Utschig, Ludwig Weiler, Rongjun Xie, Andre Zimmermann, Ruzhong Zuo, and many others have contributed to the fun in our group and the excellent working environment. Our visitors Didier Rescamp, Arnab Chattopadhyay, Thomas Karastamatis, Jaqueline Menchaca, William Oates, ami many others brought their work and the in ternational stimulus into our group. Furthermore I would like to welcome our new team members Nina Balke, Thorsten Schlegel, and Ilona Westram in their endeavors of ferroelectrics research. I would then like to very much appreciate the exceptional collaboration with Christopher S. Lynch from the George Woodruff School of Mechanical Engineering at the Georgia Institute of Technology, Atlanta, Georgia. His and his family's hospitality during my several visits to Atlanta and the long X Acknowledgement lasting scientific conversations in the lab, in the office, and late at night made me feel welcome and respected wherever and whenever we met. I thank Qiming Zhang from the Materials Research Laboratory at the Pennsylvania State University, who hosted me during my first footsteps into ferroelectricity and gave me the possibility to enjoy the spirit of the largest school in ferroelectrics in the world. I furthermore thank Hideaki Aburatani from the same school for sharing his knowledge on acoustic emission of fer roelectrics. And I thank the entire team at the MRL in PennState for much fun and the tale-gating in the snow. I then thank Vladimir and Alevtina Shur from the Ural State Univer sity in Ekatherinburg in Russia for the friendly and fruitful collaboration on the discontinuous processes in ferroelectric single crystals and the excellent crystals they provided for our measurements. Other collaborators from all over the world have contributed: Marialme Hammer, Axel Endriss, Alexandre Glazounov, Michael Hoffmann and Jan Reszat from the Universität Karlsruhe, Ute Bahr, Hans-Achim Bahr, Herhert Balke, Bak Pham from the Technische Universität Dresden, Mare Kamlah, Theo Fett, and Dietrich Munz from the Forschungszentrum Karlsruhe, Ute Rabe and Walter Arnold from the Universität Saarbrücken, Hans-Joachim Kleebe from the Universität Bayreuth, Michael Schröder from the Institut für Physkalische Chemie, TU Darmstadt, and Markus Kreuzer from the Institut für Angewandte Physik, TU Darmstadt. I would also like to acknowledge our new and already so fruitful collaboration with Jim Scott and his team from Cambridge. I am then very much indebted to the Institut für Materialwissenschaften for the excellent working environment concerning equipment, personneI, and the flexibility in work procedures in many respects. No experimental work is successful without a good workshop. Jochen Korzer and his team have furnished an outstanding quality of equipment for all our experimental ideas. All members of the Schwerpunkt programm Multifunktionswerkstoffe of the Deutsche Forschungsgemeinschaft have provided useful discussions and happyevenings. The financial support by the Deutsche Forschungsgemeinschaft is greatly acknowledged. My parents are at the source of it all. They raised me lovingly and initiated an interest in science and technology in an early stage of my life. My brot her has been a constant joy throughout. Last, but not least, I would like to express my love to rny wife Kathrin, who has been so patient in the course of rnanuscript writing and beyond. Contents Symbols and Abbreviations ................................... XV 1 Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1 1.1 Document Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1 1.2 Fatigue................................................ 1 1.3 Historieal.............................................. 2 1.4 Ferroeleetrieity and Piezoelectrieity . . . . . . . . . . . . . . . . . . . . . . . 4 1.5 The Lead-Zireonate-Titanate Crystal System .............. 8 1.5.1 Dopants......................................... 8 1.5.2 PIC 151 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 10 1.5.3 Lanthanum Doped PZT . . . . . . . . .. . . . . . . . . .. . . . . . .. 11 1.6 Defeets in PZT . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 14 1.6.1 Vaeaneies and Interstitials . . . . . . . . . . . . . . . . . . . . . . . .. 14 1.6.2 Thermal Equilibrium ............................. 14 1.6.3 The Quenehed State . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 16 1.7 Maeroseopie Fatigue . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 18 1.8 Point Defeets and Fatigue .... . . . . . . . . . . . . . . . . . . . . . . . . . .. 20 1.9 Domain Pinning, Aging, and Imprint ..................... 23 1.10 Eleetrodes and Thin Films. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 27 1.11 Crystal- and Mierostrueture ............................. 32 1.12 Temperature Dependenee of Fatigue .. . . . . . . . . . . . . . . . . . . .. 33 1.13 Switehing, Relaxation, and Rate Dependeneies . . . . . . . . . . . .. 34 1.14 Mieroeraeking. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 35 1.15 Models. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . .. 36 1.16 Fatigue-Free Systems ................................... 39 2 Macroscopic Phenomenology ............................. 41 2.1 Fatigue and Measurement Proeedures . . . . . . . . . . . . . . . . . . . .. 41 2.2 Polarization and Strain Loss . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 43 2.3 Asymmetry and Offset-Polarization . . . . . . . . . . . . . . . . . . . . . .. 46 2.3.1 Strain Asymmetry. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 46 2.3.2 Obstacles to 90° Domain Switehing . . . . . . . . . . . . . . . .. 48 2.4 Anisotropy............................................ 51 2.5 Leakage Current, Sample Coloring, and Relaxation .. . . . . . .. 55