FERROELECTRICS – PHYSICAL EFFECTS Edited by Mickaël Lallart Ferroelectrics – Physical Effects Edited by Mickaël Lallart Published by InTech Janeza Trdine 9, 51000 Rijeka, Croatia Copyright © 2011 InTech All chapters are Open Access articles distributed under the Creative Commons Non Commercial Share Alike Attribution 3.0 license, which permits to copy, distribute, transmit, and adapt the work in any medium, so long as the original work is properly cited. After this work has been published by InTech, authors have the right to republish it, in whole or part, in any publication of which they are the author, and to make other personal use of the work. Any republication, referencing or personal use of the work must explicitly identify the original source. Statements and opinions expressed in the chapters are these of the individual contributors and not necessarily those of the editors or publisher. No responsibility is accepted for the accuracy of information contained in the published articles. The publisher assumes no responsibility for any damage or injury to persons or property arising out of the use of any materials, instructions, methods or ideas contained in the book. Publishing Process Manager Silvia Vlase Technical Editor Teodora Smiljanic Cover Designer Jan Hyrat Image Copyright 2010. Used under license from Shutterstock.com First published July, 2011 Printed in Croatia A free online edition of this book is available at www.intechopen.com Additional hard copies can be obtained from orders@intechweb.org Ferroelectrics – Physical Effects, Edited by Mickaël Lallart p. cm. ISBN 978-953-307-453-5 free online editions of InTech Books and Journals can be found at www.intechopen.com Contents Preface IX Part 1 General Ferroelectricity 1 Chapter 1 Morphotropic Phase Boundary in Ferroelectric Materials 3 Abdel-Baset M. A. Ibrahim, Rajan Murgan, Mohd Kamil Abd Rahman and Junaidah Osman Chapter 2 Relaxor-ferroelectric PMN–PT Thick Films 27 Hana Uršič and Marija Kosec Chapter 3 Phase Diagramm, Cristallization Behavior and Ferroelectric Properties of Stoichiometric Glass Ceramics in the BaO-TiO 2 -B 2 O 3 System 49 Rafael Hovhannisyan, Hovakim Alexanyan, Martun Hovhannisyan, Berta Petrosyan and Vardan Harutyunyan Chapter 4 Ferroelectric Properties and Polarization Switching Kinetic of Poly (vinylidene fluoride-trifluoroethylene) Copolymer 77 Duo Mao, Bruce E. Gnade and Manuel A. Quevedo-Lopez Chapter 5 Charge Transport in Ferroelectric Thin Films 101 Lucian Pintilie Chapter 6 Hydrogen in Ferroelectrics 135 Hai-You Huang, Yan-Jing Su and Li-Jie Qiao Chapter 7 Thermal Conduction Across Ferroelectric Phase Transitions: Results on Selected Systems 155 Jacob Philip Chapter 8 The Induced Antiferroelectric Phase - Structural Correlations 177 Marzena Tykarska VI Contents Part 2 Piezoelectrics 193 Chapter 9 Piezoelectric Effect in Rochelle Salt 195 Andriy Andrusyk Chapter 10 Piezoelectricity in Lead-Zirconate-Titanate Ceramics – Extrinsic and Intrinsic Contributions 221 Johannes Frantti and Yukari Fujioka Chapter 11 B-site Multi-element Doping Effect on Electrical Property of Bismuth Titanate Ceramics 243 Jungang Hou and R. V. Kumar Part 3 Magnetoelectrics and Multiferroics 275 Chapter 12 Magnetoelectric Multiferroic Composites 277 M. I. Bichurin, V. M. Petrov and S.Priya Chapter 13 Coupling Between Spins and Phonons Towards Ferroelectricity in Magnetoelectric Systems 303 J. Agostinho Moreira and A. Almeida Chapter 14 Ferroelectric Field Effect Control of Magnetism in Multiferroic Heterostructures 329 Carlos A. F. Vaz and Charles H. Ahn Chapter 15 Effects of Doping and Oxygen Nonstoichiometry on the Thermodynamic Properties of Some Multiferroic Ceramics 347 Speranta Tanasescu, Alina Botea and Adelina Ianculescu Chapter 16 Multifunctional Characteristics of B-site Substituted BiFeO 3 Films 373 Hiroshi Naganuma Part 4 Liquid Crystals and Optical Effects 405 Chapter 17 Ferroelectric Liquid Crystals with High Spontaneous Polarization 407 Slavomír Pirkl and Milada Glogarová Chapter 18 Ferroelectric Liquid Crystals Composed of Banana-Shaped Thioesters 429 Stanisław Wróbel, Janusz Chruściel, Marta Wierzejska-Adamowicz, Monika Marzec, Danuta M. Ossowska-Chruściel, Christian Legrand and Redouane Douali Contents VII Chapter 19 Molecular Design of a Chiral Oligomer for Stabilizing a Ferrielectric Phase 449 Atsushi Yoshizawa and Anna Noji Chapter 20 Memory Effects in Mixtures of Liquid Crystals and Anisotropic Nanoparticles 471 Marjan Krašna, Matej Cvetko, Milan Ambrožič and Samo Kralj Chapter 21 Photorefractive Ferroelectric Liquid Crystals 487 Takeo Sasaki Chapter 22 Linear and Nonlinear Optical Properties of Ferroelectric Thin Films 507 Bing Gu and Hui-Tian Wang Chapter 23 Localized States in Narrow-Gap Ferroelectric-Semiconductor PbSnTe: Injection Currents, IR and THz Photosensitivity, Magnetic Field Effects 527 Alexander Klimov and Vladimir Shumsky Chapter 24 Piezo-optic and Dielectric Behavior of the Ferroelectric Lithium Heptagermanate Crystals 553 A. K. Bain, Prem Chand and K. Veerabhadra Rao Chapter 25 Compositional and Optical Gradient in Films of PbZr x Ti 1-x O 3 (PZT) Family 579 Ilze Aulika, Alexandr Dejneka, Silvana Mergan, Marco Crepaldi, Lubomir Jastrabik, Qi Zhang, Andreja Benčan, Maria Kosec and Vismants Zauls Chapter 26 Photo-induced Effect in Quantum Paraelectric Materials Studied by Transient Birefringence Measurement 603 Toshiro Kohmoto and Yuka Koyama Chapter 27 Photoluminescence in Doped PZT Ferroelectric Ceramic System 619 M. D. Durruthy-Rodríguez and J. M. Yáñez-Limón Chapter 28 Photovoltaic Effect in Ferroelectric LiNbO 3 Single Crystal 641 Zhiqing Lu, Kun Zhao and Xiaoming Li Preface Ferroelectricity has been one of the most used and studied phenomena in both scientific and industrial communities. Properties of ferroelectrics materials make them particularly suitable for a wide range of applications, ranging from sensors and actuators to optical or memory devices. Since the discovery of ferroelectricity in Rochelle Salt (which used to be used since 1665) in 1921 by J. Valasek, numerous applications using such an effect have been developed. First employed in large majority in sonars in the middle of the 20 th century, ferroelectric materials have been able to be adapted to more and more systems in our daily life (ultrasound or thermal imaging, accelerometers, gyroscopes, filters…), and promising breakthrough applications are still under development (non-volatile memory, optical devices…), making ferroelectrics one of tomorrow’s most important materials. The purpose of this collection is to present an up-to-date view of ferroelectricity and its applications, and is divided into four books: Material Aspects, describing ways to select and process materials to make them ferroelectric. Physical Effects, aiming at explaining the underlying mechanisms in ferroelectric materials and effects that arise from their particular properties. Characterization and Modeling, giving an overview of how to quantify the mechanisms of ferroelectric materials (both in microscopic and macroscopic approaches) and to predict their performance. Applications, showing breakthrough use of ferroelectrics. Authors of each chapter have been selected according to their scientific work and their contributions to the community, ensuring high-quality contents. The present volume is interested in the explanation of the physical mechanisms that lie in ferroelectrics, and the associated effects that make ferroelectric materials so interest- ing in numerous applications. After a general introduction on ferroelectric and ferroelectric materials (chapters 1 to 8), the book will focus on particular effects associated with ferroelectricity: piezoelec- X Preface tricity (chapters 9 to 11), optical properties (chapters 12 to 16), and multiferroic and magnetoelectric devices (chapters 17 to 28), reporting up-to-date findings in the field. I sincerely hope you will find this book as enjoyable to read as it was to edit, and that it will help your research and/or give new ideas in the wide field of ferroelectric mate- rials. Finally, I would like to take the opportunity of writing this preface to thank all the au- thors for their high quality contributions, as well as the InTech publishing team (and especially the publishing process manager, Ms. Silvia Vlase) for their outstanding support. June 2011 Dr. Mickaël Lallart INSA Lyon, Villeurbanne France [...]... = 1. 3 (thin solid curve), the maximum value of χTHG is found to be zyyz around 1. 15 × 10 12 m 2 v -2 at β* 4.5 At f = 1. 1 (the dashed curve) the maximum value of χTHG is 4.8 × 10 12 m 2 v -2 at β* 3.5 At f = 1. 01 (solid curve), the maximum value of χTHG zyyz zyyz increases to 9 .1 × 10 12 m 2 v -2 at β* 3 At f = 0.9 (the -●- curve), the maximum value of χTHG further increases to 1. 61 × 10 11 ... Lett 79, 400 (20 01) Cross L., Ferroelectrics 76, 2 41 (19 87) Cross L., Ferroelectrics 15 1, 305 (19 94) Eaton D F., Science, New Series, Vol 253, No 5 017 , 2 81 (19 91) Fu H., Cohen R., Nature 403, 2 81 (2000) Glass A M., Science, New Series, 235(4792) 10 03 (19 87) Guo R., Cross L E., Park S-E., Noheda B., Cox D E., and Shirane G., Phys Rev Lett 84, 5423 (2000) Haas C., Phys Rev 14 0, A863 (19 65) Haun M J.,... 1 ⎡α + β2 Ps2 ε0 ⎤ and ⎣ ⎦ ε zz = 1 ⎡α + 3 1 Ps2 ε 0 ⎤ (Murgan et al., 2002) Substituting ε xx and ε zz into Eq (26) yields the ⎣ ⎦ simple relation β2 = 3 1 The value of 1 is then estimated from the spontaneous polarization equation Ps = −ε0 α 1 in tetragonal phase This yields 1 = 7.58 × 10 14 m 3 J -1 for Ps ≈ 0.26 C.m-2 at room temperature Hence, a value of β2 = 3 1 = 2.27 × 10 13 m 3 J -1. .. operating frequency Particularly, at f = 0.3 (curve ii), the maximum value of χSHG is found to be around 4.8 × 10 −3 mv -1 at zyy 20 Ferroelectrics – Physical Effects β* 1. 2 At f = 0.5 (curve iii), the maximum value of χSHG was found to be around zyy 3.5 × 10 −3 mv -1 at β* 1. 5 At f = 0.6 (curve iv), the maximum value of χSHG was found to be zyy around 1. 5 × 10 −3 mv -1 at β* 1. 7 At f = 0.7 (curve... ⎦ ⎡ 18 β ⎤ 1 3 s ( ω) s * ( ω) ⎢ 2 1 Ps2 s ( 0 ) − 1 3 ε0 ⎣ ε0 ⎦ (19 ) ⎡ 3 P 2β β s ( 0 ) + β2 Ps 2 σ ( 0 ) ⎤ β2 2 σ ( ω) s ( ω) s * ( ω) ⎢ s 1 2 ⎥ 3 2 ε0 ε0 ⎣ ⎦ (20) ⎡ 2 P 2β σ ( 0 ) 1 ⎤ β2 2 σ ( ω) s ( ω) s * ( ω) ⎢ s 22 − ⎥ 3 ε0 ε0 3⎦ ⎣ ( 21) ⎡ 3β P 2 s ( 0 ) + β2 Ps 2 σ ( 0 ) 1 ⎤ β2 2 − ⎥ s ( ω ) σ ( ω ) σ * ( ω) ⎢ 1 s 3 2 ε0 ε0 3⎦ ⎣ (22) 3) IP 3) IP χ(zyyz = χ(zxxz = ~ ( 3) IP (17 ) ⎡ 2β P 2 1 β2... mε0 ωTO ⎡ ⎦ (30) 1 2 χ(zz) = − 1 ⎣ 2 a (T − Tc ) ⎦ = 1 ε0 mωLO ⎡ ⎤ ( 31) 1 In Eq (29) and (30), the static linear dielectric constant shows that at the MPB, χ(xx) ( ω → 0 ) ( 1) ( 1) and χ yy ( ω → 0 ) diverge when 1 = β2 at all temperatures while χ zz ( ω → 0 ) diverges only at 1 T → Tc In Fig 5(a), we plot the complex dynamic dielectric susceptibility χ(xx) versus 1 * β = β2 1 at single operating... (THG) K =1 4 Symmetric on interchange of ( lmn ) 3 )THG χ(zzzz = ~ ( 3 )THG ~ ( 3 )THG χ xxzz ~ ( 3 )THG χ zyyz ~ ( 3 )THG = χ yyzz ~ ( 3 )THG = χ zxxz ⎡ 18 Ps2 1 ⎤ 1 s ( 3ω) s 3 ( ω) ⎢ s ( 2 ω) − 1 3 2 ε0 ⎣ ε0 ⎦ ~ ( 3 )THG χ yxxy = χ xxyy = = ⎡ 4β P 2 σ ( 2ω) + 6 1 Ps2 s ( 2ω) ⎤ 1 β2 s ( 3ω ) σ 2 ( ω ) s ( ω ) ⎢ 2 s − 1 3 2 ε0 3 ε0 ⎣ ⎦ (14 ) ⎡2 2 ⎤ 1 * σ ( ω) σ 3 ( ω) ⎢ 2 β2 Ps2 s ( 0 ) − 1 ⎥ 3 ε0... permittivity, 6 Ferroelectrics – Physical Effects piezoelectric coefficients and the electromechanical coupling factors of PZT at room temperature occur at this MPB (Jaffe et al., 19 71) However, the maximum value of the remanent polarization is shifted to smaller Ti contents For ferroelectrics with rhombohedral and tetragonal symmetries on the two sides of the MPB, the polar axes are (1, 1 ,1) and (0,0 ,1) (Noheda... yyzz = χ xxzz = χ zzyy = χ zzxx = (16 ) (18 ) ~ ( 3) IP 3) IP 3) IP χ(yzzy = χ(xzzx = ~ ( 3) IP β2 3 σ ( ω) σ * ( ω) 3 3ε 0 (15 ) ⎡ 2β P 2 s ( 0 ) 2 ⎤ β2 3 σ ( ω ) σ * ( ω) ⎢ 2 s 2 − ⎥ 3 ε0 2ε0 3⎦ ⎣ ~ ( 3) IP χ xxyy = χ yyxx = ~ ( 3) IP (12 ) (13 ) 3) IP 3) IP χ(yxxy = χ(xyyx = − ~ ( 3) IP (11 ) ⎡ 4β P 2 σ ( 2 ω) + 6 1 Ps2 s ( 2 ω) ⎤ 1 β2 σ ( 3ω ) σ ( ω ) s 2 ( ω ) ⎢ 2 s − 1 3 2 ε0 3 ε0 ⎣ ⎦ 3) χ(zzzzIP =... Malaysia as visiting scientists 11 References Ahart M., Somayazulu M., Cohen R E., Ganesh P., Dera P., Mao H-k, Hemley R J., Ren Y., Liermann P and Wu Z Nature 4 51, 545 ( 2008) Amin A., Newnhan R.E., and Cross L.E., Phys Rev B 34 15 95 (19 86) Bellaiche L and Vanderbilt D., Phys Rev Lett 83 13 47 (19 99) Cao W., and Cross L.E., Phys Rev B 47 4285 (19 93) Cohen, R E., Nature 4 41, 9 41 (2006) Cox D E., Noheda B., . (chapters 1 to 8), the book will focus on particular effects associated with ferroelectricity: piezoelec- X Preface tricity (chapters 9 to 11 ), optical properties (chapters 12 to 16 ), and. FERROELECTRICS – PHYSICAL EFFECTS Edited by Mickaël Lallart Ferroelectrics – Physical Effects Edited by Mickaël Lallart . 2 011 Dr. Mickaël Lallart INSA Lyon, Villeurbanne France Part 1 General Ferroelectricity 1 Morphotropic Phase Boundary in Ferroelectric Materials Abdel-Baset M. A. Ibrahim 1 ,