Iowa State University Capstones, Theses and Retrospective Theses and Dissertations Dissertations 2007 Phase transitions in Sn-modified lead zirconate titanate antiferroelectric ceramics Hui He Iowa State University Follow this and additional works at: https://lib.dr.iastate.edu/rtd Part of the Condensed Matter Physics Commons, and the Materials Science and Engineering Commons Recommended Citation He, Hui, "Phase transitions in Sn-modified lead zirconate titanate antiferroelectric ceramics" (2007). Retrospective Theses and Dissertations. 15923. https://lib.dr.iastate.edu/rtd/15923 This Dissertation is brought to you for free and open access by the Iowa State University Capstones, Theses and Dissertations at Iowa State University Digital Repository. It has been accepted for inclusion in Retrospective Theses and Dissertations by an authorized administrator of Iowa State University Digital Repository. For more information, please contact [email protected]. Phase transitions in Sn-modified lead zirconate titanate antiferroelectric ceramics by Hui He A dissertation submitted to the graduate faculty in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY Major: Materials Science and Engineering Program of Study Committee: Xiaoli Tan, Major Professor Ashraf F. Bastawros Matthew J. Kramer R. William McCallum Joerg Schmalian Iowa State University Ames, Iowa 2007 Copyright © Hui He, 2007. All rights reserved. UMI Number: 3274865 Copyright 2007 by He, Hui All rights reserved. UMI Microform 3274865 Copyright 2007 by ProQuest Information and Learning Company. All rights reserved. This microform edition is protected against unauthorized copying under Title 17, United States Code. ProQuest Information and Learning Company 300 North Zeeb Road P.O. Box 1346 Ann Arbor, MI 48106-1346 ii Dedicated to my parents and Hang Yan for their love and support during my education iii Table of Contents Abstract …………………………………………...…………………………………….vi 1. Introduction .......................................................................................................... 1 1.1 Perovskite Structure ........................................................................................... 1 1.2 Ferroelectricity (FE) and Antiferroelectricity (AFE) ......................................... 3 1.3 The Antiferroelectric to Ferroelectric Phase Transitions.................................... 5 1.4 PZT (Lead Zirconate Titanate) System .............................................................. 7 1.5 Sn-Modified Antiferroelectric PZT System ..................................................... 10 1.6 Incommensurate Modulations in Perovskite..................................................... 12 1.6.1 Effect of Chemical Compositions ............................................................ 14 1.6.2 Effect of Temperature .............................................................................. 17 1.6.3 Effect of Electric Fields ........................................................................... 18 1.7 Materials System for This Thesis .................................................................... 19 1.8 Key Experimental Approach ............................................................................ 20 1.8.1 Transmission Electron Microscopy ......................................................... 21 1.8.2 Raman Spectroscopy ................................................................................ 22 1.9 Applications of Antiferroelectric to Ferroelectric Transition .......................... 23 1.10 Reference………………………………………………………………............27 2. In situ Transmission Electron Microscopy Study of the Electric Field- induced Transformation of Incommensurate Modulations in a Sn-modified Lead Zirconate Titanate Ceramic .................................................................... 33 2.1 Abstract ............................................................................................................ 33 2.2 Introduction ...................................................................................................... 34 2.3 Experimental Procedure ................................................................................... 35 2.4 Results .............................................................................................................. 36 2.5 Discussion ........................................................................................................ 38 2.6 Conclusion ....................................................................................................... 39 2.7 Acknowledgements .......................................................................................... 39 2.8 Figure List ........................................................................................................ 40 iv 2.9 Reference ......................................................................................................... 44 3. Electric Field-induced Transformation of Incommensurate Modulations in Antiferroelectric Pb0.99Nb0.02[(Zr1-xSnx)1-yTiy]O3.......................................................................46 3.1 Abstract ............................................................................................................ 46 3.2 Introduction ...................................................................................................... 47 3.3 Experimental Procedure ................................................................................... 49 3.4 Results .............................................................................................................. 51 3.4.1 Average Structure and Electrical Properties ............................................ 51 3.4.2 The Incommensurate Modulation ............................................................ 52 3.4.3 In situ TEM Study .................................................................................... 54 3.5 Discussion ........................................................................................................ 57 3.6 Conclusion ....................................................................................................... 64 3.7 Acknowledgements .......................................................................................... 65 3.8 Figure List ........................................................................................................ 65 3.9 Table List ......................................................................................................... 66 3.10 Reference ......................................................................................................... 77 4. Raman spectroscopy study of the phase transitions in Pb0.99Nb0.02[(Zr0.57Sn0.43)1-yTiy]0.98O3 ceramics ................................................. 79 4.1 Abstract ............................................................................................................ 79 4.2 Introduction...................................................................................................... 80 4.3 Experimental Procedure................................................................................... 81 4.4 Results and Discussion .................................................................................... 83 4.4.1 Structure and Electrical Properties........................................................... 83 4.4.2 Raman Spectroscopy Studies................................................................... 86 4.5 Conclusion ....................................................................................................... 90 4.6 Acknowledgements .......................................................................................... 90 4.7 Figure List ........................................................................................................ 91 4.8 Reference ....................................................................................................... 105 5. Phase Transition Toughening in Sn-Modified Lead Zirconate Titanate Antiferroelectric Ceramics .............................................................................. 107 5.1 Abstract .......................................................................................................... 107 v 5.2 Introduction .................................................................................................... 108 5.3 Experimental Procedure ................................................................................. 109 5.4 Results ............................................................................................................ 111 5.4.1 Structure and Electrical Properties ......................................................... 111 5.4.2 Electric field-induced fracture ............................................................... 113 5.5 Discussion ...................................................................................................... 114 5.6 Conclusion ..................................................................................................... 116 5.7 Figure List ...................................................................................................... 117 5.8 Reference ....................................................................................................... 127 6 General Conclusions ........................................................................................ 129 7 Recommendations for Further Study ...........................................................