FERROELECTRICS – MATERIAL ASPECTS Edited by Mickaël Lallart Ferroelectrics – Material Aspects 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 Noel Powell, Schaumburg, 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 – Material Aspects, Edited by Mickaël Lallart p. cm. ISBN 978-953-307-332-3 free online editions of InTech Books and Journals can be found at www.intechopen.com Contents Preface IX Part 1 Preparation and Synthesis 1 Chapter 1 BST and Other Ferroelectric Thin Films by CCVD and Their Properties and Applications 3 Yongdong Jiang, Yongqiang Wang, Kwang Choi Deepika Rajamani and Andrew Hunt Chapter 2 Synthesis of Ferroelectric Na 0.5 Bi 0.5 TiO 3 by MSS (Molten Salt Synthesis) Method 31 Teresa Zaremba Chapter 3 Electrical Characterizations of Lead Free Sr and Sn Doped BaTiO 3 Ferroelectric Films Deposited by Sol-Gel 49 Jean-Claude Carru, Manuel Mascot and Didier Fasquelle Chapter 4 Control of Crystallization and Ferroelectric Properties of BaTiO 3 Thin Films on Alloy Substrates 73 Zhiguang Wang, Yaodong Yang, Ravindranath Viswan, Jie-Fang Li and D. Viehland Chapter 5 Growth and Characterization of Single Crystals of Potassium Sodium Niobate by Solid State Crystal Growth 87 Andreja Benčan, Elena Tchernychova, Hana Uršič, Marija Kosec and John Fisher Chapter 6 Deposition of CoFe 2 O 4 Composite Thick Films and Their Magnetic, Electrical Properties Characterizations 109 W. Chen and W. Zhu Chapter 7 Studies on Electrical and Retention Enhancement Properties of Metal-Ferroelectric-Insulator-Semiconductor with Radical Irradiation Treatments 129 Le Van Hai, Takeshi Kanashima and Masanori Okuyama VI Contents Chapter 8 Performance Enhanced Complex Oxide Thin Films for Temperature Stable Tunable Device Applications: A Materials Design and Process Science Prospective 149 M.W. Cole and S.P. Alpay Part 2 Doping and Composites 179 Chapter 9 The Effect of Mn Doping on the Dielectric Properties of Lead Strontium Titanate (PST) 181 Arne Lüker, Qi Zhang and Paul B. Kirby Chapter 10 Enhanced Electro-Optical Properties of Liquid Crystals Devices by Doping with Ferroelectric Nanoparticles 193 Hao-Hsun Liang and Jiunn-Yih Lee Chapter 11 Ferroelectric-Dielectric Solid Solution and Composites for Tunable Microwave Application 211 Yebin Xu and Yanyan He Chapter 12 New Multiferroic Materials: Bi 2 FeMnO 6 237 Hongyang Zhao, Hideo Kimura, Qiwen Yao, Yi Du, Zhenxiang Cheng and Xiaolin Wang Chapter 13 Lead Titanate-Based Nanocomposite: Fabrication, Characterization and Application and Energy Conversion Evaluation 251 Walter Katsumi Sakamoto, Gilberto de Campos Fuzari Jr, Maria Aparecida Zaghete and Ricardo Luiz Barros de Freitas Part 3 Lead-Free Materials 277 Chapter 14 Barium Titanate-Based Materials – a Window of Application Opportunities 279 Daniel Popovici, Masanori Okuyama and Jun Akedo Chapter 15 Lead-Free Ferroelectric Ceramics with Perovskite Structure 305 Rigoberto López-Juárez, Federico González and María-Elena Villafuerte-Castrejón Chapter 16 Synthesis of PZT Ceramics by Sol-Gel Method and Mixed Oxides with Mechanical Activation Using Different Oxides as a Source of Pb 331 J. M. Yáñez-Limón, G. Rivera-Ruedas, F. Sánchez De: Jesús, A. M. Bolarín-Miró, R. Jiménez Riobóo and J. Muñoz-Saldaña Chapter 17 Flexible Ferroelectric BaTiO 3 – PVDF Nanocomposites 347 V. Corral-Flores and D. Bueno-Baqués Contents VII Chapter 18 Epitaxial Integration of Ferroelectric BaTiO 3 with Semiconductor Si: From a Structure- Property Correlation Point of View 363 Liang Qiao and Xiaofang Bi Chapter 19 Nanostructured LiTaO 3 and KNbO 3 Ferroelectric Transparent Glass-Ceramics for Applications in Optoelectronics 389 Anal Tarafder and Basudeb Karmakar Chapter 20 Ferroelectricity in Silver Perovskite Oxides 413 Desheng Fu and Mitsuru Itoh Part 4 Thin Films 443 Chapter 21 Amino-Acid Ferroelectric Thin Films 445 Balashova E.V. and Krichevtsov B.B. Chapter 22 BiFeO 3 Thin Films Prepared by Chemical Solution Deposition with Approaches for Improvement of Ferroelectricity 479 Yoshitaka Nakamura, Seiji Nakashima and Masanori Okuyama Chapter 23 Strontium Barium Niobate Thin Films for Dielectric and Electro-Optic Applications 497 Mireille Cuniot-Ponsard 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 aims at exposing the material aspects of ferroelectric materials, focusing on synthesis (chapters 1 to 8), emphasizing the importance of adapted methods to obtain high-quality materials; effect of doping and composite design and growth (chapters 9 to 13), showing how the ferroelectric activity may be significantly enhanced by the addition of well-chosen materials; lead-free materials (chapters 14 to 20), addressing the importance of environmentally friendly devices; and ferroelectric X Preface thin films (chapters 21 to 23), which show particular effects due to their size and attracted much attention over the last few years. 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 materials. Finally, I would like to take the opportunity of writing this preface to thank all the authors 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 [...]... loss of 1. 8 - 5.4 dB and a tuning of 12 .6% are achieved in frequency range of 9.3 – 10 .1 GHz  21 BST and Other Ferroelectric Thin Films by CCVD and Their Properties and Applications 0 0 (a) -5 S 21 (10 V) -5 S 21 (20 V) S 21 (30 V) -10 S 11 (dB) -10 S 21 (dB) (b) S 21 (0 V) -15 -15 -20 -20 -25 -25 -30 -30 S 11 (0 V) S 11 (10 V) S 11 (20 V) S 11 (30 V) 6 8 10 12 14 16 18 6 8 10 Frequency (GHz) 16 18 0 S 21 (0 V)... (c) (d) S 21 (10 V) S 21 (20 V) -10 S 21 (30 V) -20 S 11 (dB) S 21 (dB) 14 Frequency (GHz) 0 -10 12 -30 -20 S 11 (0 V) -30 -40 S 11 (10 V) S 11 (20 V) -50 S 11 (30 V) -40 6 8 10 12 14 16 18 6 8 10 Frequency (GHz) 12 14 16 18 Frequency (GHz) Fig 22 Measured (a) insertion loss and (b) return loss of a 2-pole and (c) insertion loss and (d) return loss of a 3-pole SWR filter 0 0 -5 (b) -5 S 11 (dB) -10 S 21 (dB) (a)... 0V 5V 10 V 20 V 30 V -15 -20 -10 0V 5V 10 V 20 V 30 V -15 -25 -20 -30 8 9 10 11 12 13 14 15 Frequency (GHz) 16 17 18 8 9 10 11 12 13 14 15 16 17 18 Frequency (GHz) Fig 23 Measured (a) insertion and (b) return loss (SOLT cal) of a 2-pole low-voltage SWR filter using LVE BST capacitors The fabrication requires two 200 μm thick LCP layers originally covered by a 9 μm Cu foil The top resonators (1 and... can be grown epitaxially on SrTiO3 (10 0) or r-sapphire with (10 0) or (11 0) plane parallel to the substrate surface, respectively (Yoon et al., 19 94) 10 Ferroelectrics – Material Aspects S a p p h ir e ( 0 0 0 6 ) (1 1 1 ) P L Z T 1 7 /5 0 /5 0 (1 1 0 ) P L Z T 1 5 /5 0 /5 0 P L Z T 1 7 /4 0 /6 0 P L Z T 1 2 /4 0 /6 0 P L Z T 2 0 /3 0 /7 0 (1 0 0 ) 20 25 P L Z T 1 5 /3 0 /7 0 30 35 40 45 2  (d e g... devices 8 Ferroelectrics – Material Aspects (a) (b) Sapphire (10 4) Film (11 0) Sapphire(006) Film (11 1) /2 direction Fig 5 (a) SEM image and (b) XRD pattern of a multilayer dielectric thin film Sample ID Multilayer Single layer Capacitance and loss at 1 MHz 0V 40 V Cp (pF) Cp (pF) Tan Tan 1. 14 0.005 0.90 0.003 1. 28 0.028 0.85 0. 019 S 21 at 50 GHz (dB) Tuning (%) FOM 1. 46 - 21. 1 33.3 4820 15 37 Table... (S 11) & Insertion Loss (S 21) in dB Fig 27 Photograph of a ring filter 31. 6 G Hz -2.33 dB 0 33.7 G Hz -2.3 21 dB -5 -10 -15 -20 D B (|S (1, 1)|) 00V -25 D B (|S (2 ,1) |) 00V -30 D B (|S (1, 1)|) 30V -35 D B (|S (2 ,1) |) 30V -40 20 22 24 26 28 30 32 34 36 38 Frequency (G Hz) 40 42 44 46 48 50 Fig 28 Measured S-parameters for Ka-band ring filter under different biases (blue=S 11 and pink=S 21 at 0V; brown=S 11. .. S 21_ NB S 11_ W B S 21_ W B -50 -60 30 36 42 48 Frequency (GHz) Fig 17 Measured S parameters of 3-pole wideband and narrowband filters (no BST capacitors) 18 Ferroelectrics – Material Aspects Fig 18 A 2-pole CPW admittance inverter tunable filter with MEMS switches Insertion Loss in dB D B(|S (2 ,1) |) W B 15 v D B(|S (2 ,1) |) W B 1v D B(|S (2 ,1) |) W B 2v D B(|S (2 ,1) |) 32 97 G Hz W B 20v -10 3 9 dB D B(|S (2 ,1) |)... PLZT 17 /40/60, and PLZT 17 /50/50 thin films show only (11 1) peaks, indicating that these films inherited the epitaxy of PLT seed layer and were grown epitaxially on c-sapphire substrate with (11 1) plane parallel to the substrate surface However, the XRD pattern of the PLZT 15 /30/70 film shows small extra peaks of (10 0) and (11 0), and those of the PLZT 12 /40/60 and PLZT 15 /50/50 films show extra (11 0)... achieved In addition, due to the increased effective 20 Ferroelectrics – Material Aspects Parameter Tx to antenna frequency fange Insertion loss Return loss Attenuation at Rx Antenna to Rx frequency range Insertion loss Return loss Attenuation at Tx Tx to Rx isolation 18 50 -19 10 19 30 -19 90 Values 18 50 – 19 10 MHz 2 dB max 12 dB 40 dB 19 30 – 19 90 MHz 2.0 dB max 12 dB 45 dB 50 dB 40 dB Table 4 Typical specifications... 1) |) N B 8v -2 0 DB (|S(2 , 1) |) NB 40 v DB (|S (2, 1 )|) NB 1 5v D B (| S (2 , 1) |) N B 2v 30.8 G Hz -1 7.48 dB DB (|S (2, 1 )|) NB 10 v D B (| S (2 , 1) |) N B 5v -1 0 D B (| S (2 , 1) |) N B 0v D B (| S (2 , 1) |) N B 1v (b) DB (|S (2, 1 )|) NB 3 0v -3 0 -4 0 -5 0 -6 0 25 30 35 F re qu en c y (G H z ) 40 45 Fig 19 Measured insertion loss, S 21, of a 2-pole CPW admittance inverter filter with MEMS switches . and has (11 1) plane parallel to the substrate surface. The orientation relationship between the BST film and c-sapphire substrate is BST (11 1)//sapphire (00 01) and BST [11 0]//sapphire [10 4]. The. that there are only (11 1) peak of the BST film and (006) peak of sapphire along the /2 direction. The (11 0) and (11 1) peaks of the BST film appear as dots and align with (10 4) and (006) peaks. FOM 0 V 40 V Cp (pF) Tan Cp (pF) Tan Multilayer 1. 14 0.005 0.90 0.003 1. 46 21. 1 4820 Single layer 1. 28 0.028 0.85 0. 019 - 33.3 15 37 Table 2. Comparison of electrical properties between