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    Sodium Potassium Niobate-based Lead-free Piezoelectric Ceramics: Bulk and

    Freestanding Thick Films

    A Thesis

    Submitted to the Faculty

    of

    Drexel University

    by

    Huidong Li

    in partial fulfillment of the

    requirements for the degree

    of

    Doctor of Philosophy

    June 2008

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    Copyright 2008

    Huidong Li. All Rights Reserved.

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    ii

    Dedications

    To my beloved wife and parents.

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    iii

    Acknowledgements

    Nearly five years of hard work combined with the great help and assistance

    from people around me made it possible for me to finish this thesis work. I especially

    would like to express my most sincere gratitude my advisors, Drs. Wei-Heng Shih

    and Wan Y. Shih who have guided me through these years for all the support, advices

    and inspiration.

    In the past a few years, I have been also really grateful to be able to work

    alongside with the members of the ceramic processing and sensor group: Dr. Hongyu

    Luo, Dr. Zuyan Shen, Yi-Shih Chiu, Dr. Qiang Zhao, Christian Martorano, Jose

    Bermudez, Xiaotong Gao Joseph Capobianco, Hakki Yegingil, John-Paul McGovern,

    Qing Zhu and Hui Li. Their valuable input and the tremendous help in experiments

    have been an indispensible contribution to this thesis and I truly enjoy working with

    them. I specially want to thank Christian Martorano for his generous help in casting

    the lead-free tapes. I would not be able to accomplish a big part of my thesis work

    without it.

    There are also a group of people outside of our group who provided generous

    help in the course of my Ph.D. study. I would like to give special thanks to Dee

    Breger and Dr. Edward Basgall for their help in SEM and EDS analysis, Dr. Zhorro

    Nikolov for XRD and Raman experiments, Dr. Peter Finkel for electroding

    (evaporation and sputtering), Judith Trachtman for her assistance and advices

    regarding graduate studies. I also thank David Stein at the University of Pennsylvania

    for his generous help with the Curie temperature measurement involved in this thesis.

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    I greatly appreciate all the critical input and valuable suggestions given by my

    committee members: Prof. Jonathan Spanier, Prof. Peter Davies at the University of

    Pennsylvania and Prof. Guoliang Yang at the Physics department.

    Finally, I would like to express my deepest appreciation to my wife Chenting

    Huang and my parents in China, who have never stopped giving me support and hope

    that held me through all the difficulties during my years of pursuing Ph.D.

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    v

    TABLE OF CONTENTS

    LIST OF TABLES ..................................................................................................... viii

    LIST OF FIGURES ..................................................................................................... ix

    ABSTRACT ............................................................................................................... xiv

    1: INTRODUCTION AND MOTIVATION ................................................................ 1

    2: INTRODUCTION OF LEAD-FREE PIEZOELECTRIC CERAMICS ANDSPECIFIC RESEARCH OBJECTIVES. ................................................................. 4

    2.1 Fundamentals of perovskite piezoelectric ceramics ......................................... 4

    2.1.1 Basics of piezoelectric materials ........................................................... 4

    2.1.2 Perovskite ferroelectrics........................................................................ 8

    2.2 Lead-based piezoelectric materials ................................................................. 10

    2.3 Current lead-free piezoelectric materials ........................................................ 11

    2.4 Current approaches to improve piezoelectrics ................................................ 16

    2.4.1 Construct solid solutions near morphotropic phase boundaries ......... 16

    2.4.2 Doping................................................................................................. 18

    2.4.3 Grain size control ................................................................................ 20

    2.4.4 Crystallographic texturing .................................................................. 20

    2.4.5 Electric-field enhanced piezoelectric coefficient of freestanding films .............................................................................................................. 22

    2.5 Sodium potassium niobate-based material systems ........................................ 28

    2.6 Specific aims of this thesis study .................................................................... 32

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    vi

    3: SYNTHESIS OF Na0.5K0.5NbO3 PIEZOELECTRICS BY A SOLUTIONCOATING APPROACH ........................................................................................ 35

    3.1 Experimental Procedure .................................................................................. 36

    3.2 NKN prepared by the coating method without sintering aid ........................... 40

    3.3 NKN prepared by the coating method with the sintering aid .......................... 46

    3.4 Chapter summary ............................................................................................ 56

    4: EFFECT OF ANTIMONY CONCENTRATION ON THE CRYSTALLINESTRUCTURE, DIELECTRIC, AND PIEZOELECTRIC PROPERTIES OF(Na0.5K0.5)0.945Li0.055Nb1-xSbxO3 SOLID SOLUTIONS .......................................... 58

    4.1 Experimental Procedure .................................................................................. 59

    4.2 Results and Discussion ................................................................................... 62

    4.2.1 Crystalline structure of the (Na0.5K0.5)0.945Li0.055Nb(1-x)SbxO3 ............ 62

    4.2.2 Microstructure of the (Na0.5K0.5)0.945Li0.055Nb(1-x)SbxO3 ceramics ...... 66

    4.2.3 Curie temperature and the orthorhombic-to-tetragonal transition

    temperature ..................................................................................................... 70

    4.2.4 Piezoelectric and dielectric properties of the (Na0.5K0.5)0.945Li0.055Nb(1-x)SbxO3............................................................................................................. 78

    4.3 Chapter summary ............................................................................................ 81

    5: CHARACTERIZATION AND ELECTRIC-FIELD ENHANCEMENT EFFECTOF (Na0.5K0.5)0.945Li0.055Nb0.96Sb0.04O3 FREESTANDING THICK FILMS ANDTHE MECHANISM STUDY ................................................................................ 83

    5.1 Tape casting ..................................................................................................... 86

    5.2 Powder and slurry preparation for NKLNSb freestanding film fabrication .... 87

    5.3 Sintering of the NKLNSb freestanding films .................................................. 88

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    vii

    5.4 Piezoelectric property characterization of the NKLNSb4 freestanding films . 95

    5.4.1 Direct measurement of d31 of the NKLNSb4 freestanding films by thelateral displacement under DC electric field ................................................... 96

    5.4.2 Measurement of d31 for NKLNSb4 freestanding film using cantileverbending .......................................................................................................... 102

    5.5 Domain switching study of the NKLNSb4 freestanding films under DCelectric fields ........................................................................................................ 111

    5.5.1 Behavior of the dielectric constant of the NKLNSb4 freestanding filmsunder DC bias ............................................................................................... 113

    5.5.2 In-situ XRD study of NKLNSb4 freestanding films under DC electric

    fields ......................................................................................................................................................................................................................................... 116

    5.6 Chapter summary .......................................................................................... 126

    6: SUMMARY AND FUTURE WORK .................................................................. 128

    6.1 Summary of results and conclusions.............................................................. 128

    6.2 Recommended future work ............................................................................ 130

    LIST OF REFERENCES .......................................................................................... 132

    APPENDIX A: DEDUCTION OF d31 USING IN-SITU XRD RESULTS OF 40-mNKLNSb4 FREESTANDING FILMS ................................................................. 140

    Vita ..................................................................................................................... 144

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    viii

    LIST OF TABLES

    Table 2.1: Electrical property comparisons between current major lead-free systems

    and PZT ....................................................................................................................... 14

    Table 2.2 Dielectric and piezoelectric properties of current NKN-based lead-freesystems ........................................................................................................................ 31

    Table 3.1 Effect of the pressing methods on properties of the NKN prepared by thecoating method ............................................................................................................ 45

    Table 3.2 Properties of NKN with sintering aid KCN prepared by the coating methodand the conventional method sintered at 1100C and 1140C for 1 hr. ...................... 52

    Table 3.3 Chemical compositions of the NKN disc sintered without sintering aid at1100C for 2 hr, calculated from the EDS spectra collected at different locations onthe sample. .................................................................................................................. 53

    Table 3.4 Properties of NKN with the sintering aid, KCN prepared by the coatingmethod and the conventional method after sintering at 1100C for 6 hr. ................... 55

    Table 4.1 EDS analysis on the plate-like grains and normal cube-shaped grains in(Na0.5K0.5)0.945Li0.055Nb0.9Sb0.1O3 ceramics ................................................................. 66

    Table 4.2 Comparison of antimony concentrations in grain boundary, liquid phaseand grains .................................................................................................................... 69

    Table 4.3 Electrical and physical properties of (Na0.5K0.5)0.945Li0.055Nb(1-x)SbxO3ceramics with x = 0-0.1 where d33, d31, kp, and tan were as defined in the text ..... 78

    Table 5.1 Chemical compositions of NKLNSb4 bulk and thick films with differentthicknesses .................................................................................................................. 94

    Table 5.2 Dielectric properties of the NKLNSb4 freestanding film at differentthicknesses ................................................................................................................ 113

    Table 5.3 XRD peak intensity changes for the four individual peaks at 44.5

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    ix

    LIST OF FIGURES

    Figure 2.1 Schematic of the perovskite structure (ABO3) ............................................ 8

    Figure 2.2 Phase diagram of lead zirconate titanate10................................................. 10

    Figure 2.3 Bismuth layer structure13 ........................................................................... 12

    Figure 2.4 Property comparisons between PZT materials and lead-free materials: (a)dielectric permittivity as a function of Curie temperature; (b) piezoelectric coefficientas a function of temperature.34 .................................................................................... 15

    Figure 2.5 Variation of room temperature piezoelectric coefficients of PZT near theMPB. ........................................................................................................................... 16

    Figure 2.6 Numbers of equivalent polar axes of ferroelectrics with different phases: (a)six [001] directions in tetragonal; (b) twelve [110] directions in orthorhombic; (c)eight [111] directions in rhombohedral....................................................................... 17

    Figure 2.7 Crystal lattice orientations within ceramic single crystals and non-texturedor ideally-textured polycrystalline ceramics. .............................................................. 21

    Figure 2.8 SEM picture of a 22m free-standing PMN-PT film51 ............................. 22

    Figure 2.9 d31 as a function of an applied DC electric field for the free-standing PMN-PT films with different thicknesses51.......................................................................... 23

    Figure 2.10 Strain vs E-field behavior for - oriented PZN-8%PT crystal.54 .... 24

    Figure 2.11 Schematic of -oriented rhombohedral crystals under variouselectric fields ............................................................................................................... 25

    Figure 2.12 In-situ XRD of (a) an unpoled and (b) poled 20m PMN-PTfreestanding film sunder various electric fields51 ....................................................... 27

    Figure 2.13 Phase diagram of KNbO3NaNbO3 solid solution.10 ............................. 29

    Figure 3.1 TGA curve of NKN power precursor prepared by the coating method .... 37

    Figure 3.2 Experimental procedure of our coating approach of synthesizing NKNwith (a) and without the sintering aid, KCN (b). ........................................................ 39

    Figure 3.3 X-ray diffraction patterns of calcined NKN powders at varioustemperatures for 1 hr from powders prepared by (a) by the coating method and (b) theconventional solid-state reaction method The PDF numbers of the labeled phases are

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    x

    030-0963 (KNbO3), 030-0872 (Nb2O5), 005-0377 (KNO3), 021-1295 (K4Nb6O17),044-0060 (Na2Nb4O11), 031-1060 (K2Nb8O21), 028-0788 (K2Nb6O16). ..................... 41

    Figure 3.4 (a) ESEM micrograph of powder (prior to calcination) obtained by theconventional method and (b) the EDS element map of the region shown in (a), (c)ESEM micrograph of powder (prior to calcination) obtained by the coating methodand (d) the EDS element map of the region shown in (c). Red: potassium; Yellow:sodium; Light blue: niobium. ...................................................................................... 42

    Figure 3.5 ESEM micrographs of NKN prepared by the coating method and sinteredat 1100C for 2 hr using two different pressing techniques: (a) by uniaxial pressingand (b) by cold isostatic pressing (CIP). ..................................................................... 44

    Figure 3.6 ESEM micrograph of NKN powders (with sintering aid): (a) made by thecoating method and calcined at 850C and (b) made by the conventional method andcalcined at the same temperature. ............................................................................... 46

    Figure 3.7 X-ray diffraction patterns of NKN prepared by the coating method and theconventional method with the sintering aid, KCN (PDF#: 041-0482), after sintering at1100C for 1 hr. ........................................................................................................... 47

    Figure 3.8 Relative bulk density (bulk density/theoretical density) versus sinteringtemperature of NKN with 0.5 mol% sintering aid, KCN, made by solution coatingapproach (open circles) and by the traditional solid-state reaction method (filledsquares). ...................................................................................................................... 48

    Figure 3.9 ESEM micrographs of NKN with KCN sintering aid prepared by thecoating method and sintered at 1020C (a), 1080C (b), 1100C (c) and 1140C (d)

    and those of NKN with KCN sintering aid prepared by the conventional solid-statereaction method and sintered at 1020C (e), 1080C (f), 1100C (g) and 1140C (h)...................................................................................................................................... 50

    Figure 3.10 EDS chemical analysis on NKN disc sintered without sintering aid at1100C for 2 hr: (a) EDS spectrum; (b) the corresponding region where the spectrumwas collected. .............................................................................................................. 53

    Figure 3.11 ESEM photograph of the NKN made by the coating method with thesintering aid, KCN, and a prolonged heat-treatment (1100C for 6 hr) ..................... 56

    Figure 4.1 XRD patterns of (Na0.5K0.5)0.945Li0.055Nb1-xSbxO3 ceramics with x = 0- 0.1

    after sintering: (a) 20-60; (b) 44-47. ..................................................................... 62

    Figure 4.2 fT versus x of the (Na0.5K0.5)0.945Li0.055Nb1-xSbxO3 solid solutions where fTdenotes the volume fraction of the tetragonal phase. The insert shows an exemplaryfour-peak de-convolution of the diffraction pattern of x = 0.6 around 45

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    xi

    Figure 4.3 ESEM micrographs of (Na0.5K0.5)0.945Li0.055Nb1-xSbxO3 solid solutions aftersintering at their optimal sintering temperatures with (a) x = 0, (b) x = 0.01, (c) x =0.02, (d) x = 0.04, (e) x = 0.06, and (f) x = 0.1. The insert (f) shows a plate-likesecond phase at x = 0.1 which was rich in Sb as indicated by EDS. .......................... 65

    Figure 4.4 Density of the (Na0.5

    K0.5

    )0.945

    Li0.055

    Nb(1-x)

    SbxO

    3ceramic as a function of x.

    ..................................................................................................................................... 67

    Figure 4.5 Liquid phase observed in samples: (a) x=0.04, (b) x=0.06 and (c) x=0.10...................................................................................................................................... 68

    Figure 4.6 Temperature dependence of the dielectric constant of(Na0.5K0.5)0.945Li0.055Nb(1-x)SbxO3 with x=0, 0.01, 0.02, 0.04, 0.06 and 0.10 at 100 Hz,1 kHz, 10 kHz, 100 kHz and 1 MHz. .......................................................................... 71

    Figure 4.7 Temperature dependence of dielectric constant of the(Na0.5K0.5)0.945Li0.055Nb(1-x)SbxO3 at 1 kHz .................................................................. 72

    Figure 4.8 Temperature dependence of the dielectric constant of(Na0.5K0.5)0.945Li0.055Nb(1-x)SbxO3 in a low temperature range, within which To-t isimplied by the shoulder on the curve. ......................................................................... 73

    Figure 4.9 Raman spectra of the (Na0.5K0.5)0.945Li0.055Nb(1-x)SbxO3 ceramics at roomtemperature ................................................................................................................. 74

    Figure 4.10 Wavenumbers of 1and 5 modes of (Na0.5K0.5)0.945Li0.055Nb(1-x)SbxO3 asa function of x. ............................................................................................................ 75

    Figure 4.11 Full width at half maximum of the 1and 5 modes of the(Na0.5K0.5)0.945Li0.055Nb(1-x)SbxO3 as a function of x ................................................... 76

    Figure 4.12 Tc and To-t as functions of x for the (Na0.5K0.5)0.945Li0.055Nb(1-x)SbxO3ceramics ...................................................................................................................... 77

    Figure 5.1 Schematic of a tape casting process .......................................................... 87

    Figure 5.2 A piece of 40m-thick NKLNSb film sitting on top of a Drexel logo ..... 89

    Figure 5.3 ESEM photographs of the NKLNSb free-standing films of variousthicknesses sintered at 1100C for 2 hr: the cross sections [(a): 20 m; (b): 40 m; (c):

    70 m] the surfaces [(d): 20 m; (e): 40 m; (f): 70 m] .......................................... 90

    Figure 5.4 XRD pattern comparisons of the 20 m, 40 m and 70 m NKLNSb4freestanding film fired at 1100C for 2 hr: (a) patterns of the three samples; (b) the(200) peaks of the three patterns in (a). ...................................................................... 92

    Figure 5.5 ESEM photographs of the cross sections of the 40-m [(a)] and 70-m [(b)]NKLNSb4 freestanding film used for piezoelectric property measurement. ............. 97

    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    Figure 5.6 Photograph of the NKLNSb4 strip sample for the lateral displacementmeasurement. .............................................................................................................. 99

    Figure 5.7 Strain and deduced -d31 of a 40m thick NKLNSb4 freestanding film andthe bulk material by lateral displacement measurement. .......................................... 100

    Figure 5.8 Lateral strain vs. DC electric field for the NKLNSb4 freestanding films oftwo different thicknesses........................................................................................... 102

    Figure 5.9 Schematic of the electroplating setup used to coated Cu layer onto theNKLNSb4 films ........................................................................................................ 104

    Figure 5.10 ESEM photograph of the straight edge of a NKLNSb4/Cu cantilever cutby the precision wire saw. ......................................................................................... 105

    Figure 5.11 Schematic of the NKLNSb4/Cu cantilever bending displacementmeasurement setup. ................................................................................................... 106

    Figure 5.12 Bending displacement of the cantilever tip as a function of the appliedDC electric field for two cantilevers with two different NKLNSb4/Cu thickness ratios.................................................................................................................................... 107

    Figure 5.13 Deduced d31 as a function of the applied DC electric field for twocantilevers with two different NKLNSb4/Cu thickness ratios. ................................ 108

    Figure 5.14 dielectric constant change as a function of the DC electric fieldNKLNSb4/Cu cantilevers with different NKLNSb4/Cu thickness ratios, the Sb-NKLN strip and the Sb-NKLN bulk. ........................................................................ 114

    Figure 5.15 Experimental setup of the in-situ XRD measurement for the NKLNSb4freestanding films. The insert is a photograph of a sample. ..................................... 117

    Figure 5.16 In-situ XRD patterns of an unpoled 40m NKLNSb4 freestanding film.................................................................................................................................... 118

    Figure 5.17 Peak de-convolution results for the XRD pattern of an unpoled 40-m NKLNSb4 freestanding film at different electric fields: (a) 0 kV/cm, (b) 10kV/cm and (c) 15 kV/cm........................................................................................... 119

    Figure 5.18 Proposed domain switching scenarios of the unpoled 40 m NKLNSb4

    freestanding film under the electric field for: (a) orthorhombic phase: c-domains [(I)and (II)], a-domains (III); (b) tetragonal phase: a domains (IV) c-domains (V).assuming the E field direction pointing up. .............................................................. 120

    Figure 5.19 In-situ XRD patterns of poled 40m NKLNSb4 freestanding film ...... 123

    Figure 5.20 In-situ XRD patterns of a poled 40m NKLNSb4 freestanding film at 0kV/cm after exposed under E fields of 10 kV/cm and 20 kV/cm. ............................ 124

    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    Figure 5.21 In-situ XRD patterns of unpoled NKLNSb4 bulk disc (0.55 mm thick) ........................................................................................................................................ 125

    Figure 5.22 In-situ XRD patterns of poled NKLNSb4 bulk disc (0.55 mm thick)... 126

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