FABRICATION AND CHARACTERIZATION OF CHEMICALLY MODIFIED MULTIFERROIC BISMUTH FERRITE THIN FILMS YAN FENG (M Sc) A THESIS SUBMITED FOR THE DEGREE OF DOCTOR OF PHILOSOPHY DEPARTMENT OF MECHANICAL ENGINEERING NATIONAL UNIVERSITY OF SINGAPORE 2011 Acknowledgements I would like to express my sincere gratitude to my supervisors, Prof Lu Li, and Prof Lai Man On from Department of Mechanical Engineering, National University of Singapore (NUS), and Prof Zhu Tiejun from Department of Materials Science and Engineering, Zhejiang University (ZJU) for giving me the opportunity to work on this exciting project I would especially like to thank all of them for their guidance and support throughout my PhD study at NUS I benefited from their guidance in every aspect during my Ph.D research, such as the discussions we held and intellectual suggestions they made regarding my work I am grateful for the insights and advice Prof Zeng Kaiyang shared with me His suggestions and guidance were a great help in performing piezoresponse force microscopy (PFM) and Kelvin probe force microscopy (KPFM) on the microscopic ferroelectric properties as related to the experiments in Chapter I would like to thank Prof Rü diger-A Eichel from Institut fü Physikalische Chemie, r Albert-Ludwigs-Universitä Freiburg (German) for his kind assistance and advice on t the understanding of the magnetic phase transition and magnetoelectric coupling effect via electron paramagnetic response (EPR) It is a great honor for me to have opportunity to work in his group for four months Also, I would like to thank Dr Emre Erdem and Dr Peter Jakes in this group for their kind advice and suggestions I would like to thank Prof I M.Reaney from Department of Engineering Materials, University of Sheffield for his kind assistance the understanding of the microstructure of the investigated thin films via HRTEM I I would also like to thank Dr Zhang Zhen as a collaborator All the ideas we shared and discussed have proven very useful This project would not have gone so well without his contribution at the forefront of this research I specially thank Dr Wang Shijie for his help and advice at the beginning of my studies I would like to express my gratitude for the help of my colleagues and collaborators: Dr Xiahui, Mr Wang Hailong, Mr Ye Shukai, Mr Xiao Pengfei, Miss Zhu Jing, Mr Song Bohang and other members in Prof Lu’s research group In addition, I would like to give my special thanks to the staff of Materials Science Laboratory, Department of Mechanical Engineering, and National University of Singapore Finally, I want to thank my family for their understanding, encouragement, and endless love throughout my life II Table of Contents Acknowledgements I Table of Contents III Abstract VII List of Tables VIII List of Figures IX List of Symbols and Abbreviations XVII List of Publications XVIII Chapter Introduction 1.1 Overview & Motivations 1.2 Outline Chapter Literature Review 2.1 Magnetoelectric effect and multiferroic materials 2.1.1 Magnetoelectric effect[14] 2.1.2 Multiferroics 2.1.3 Single phase multiferroics [3] 2.1.4 Multiferroic composites 10 2.2 Multiferroic BiFeO3 10 2.2.1 Structure 10 2.2.2 Ferroelectricity 12 2.2.3 Dielectric Properties 13 III 2.2.4 Magnetism 14 2.2.5 Magnetoelectric Coupling 15 2.2.6 Domains and domain walls[46] 16 2.3 Device application 18 2.3.1 Data storage [1] 18 2.3.2 Optoelectronic devices 19 2.4 Thin film deposition and characterization 21 2.4.1 Pulsed Laser Deposition (PLD) 21 2.4.2 X-Ray diffraction (XRD) 22 2.4.3 Atomic force microscopy (AFM) 22 2.4.4 Macroscopic Ferroelectric measurement 23 2.4.5 Dielectric measurement 24 2.4.6 Piezoresponse force microscopy (PFM) 25 2.4.7 Switching Spectroscopy PFM (SS-PFM) 26 2.4.8 Kelvin probe force microscopy (KPFM) 27 2.4.9 Vibration sample magnetometer (VSM) 28 2.4.10 Magnetic force microscopy (MFM) 28 Chapter Experimental Procedures 30 3.1 Fabrication of Targets 30 3.1.1 Pure BiFeO3 target 30 3.1.2 Chemically Modified BiFeO3 targets 30 3.2 Thin film growth 31 IV 3.2.1 Substrate and target cleaning 31 3.2.2 Film deposition 31 3.3 Thin film characterization 32 Chapter Pure BFO thin films 34 4.1 Introduction 34 4.2 Epitaxial BiFeO3 thin films 34 4.2.1 Structures of (001), (011) and (111) oriented BiFeO3 thin films 34 4.2.2 Surface morphology 37 4.2.3 Macroscopic electrical properties of (001), (011) and (111) oriented BiFeO3 thin films 37 4.2.4 Ferroelectric domain structure using PFM 40 4.2.5 Magnetoelectric coupling of BiFeO3 thin films via PFM and MFM 46 4.3 Polycrystalline BiFeO3 thin films 48 4.3.1 BFO on Pt/TiO2/SiO2/Si substrate 48 4.3.2 Size effect on the piezoelectric response of BFO on Pt/TiO2/SiO2/Si substrate 56 4.4 Effects of bottom electrode on switching behavior at nanoscale 61 4.4.1 Structure and multiferroic properties of BFO on LaNiO3/Si and SrRuO3/Si substrates 61 4.5 Effect of bottom electrode on the surface potential of polycrystalline BFO 70 Chapter Chemically modified BFO thin films 74 5.1 Introduction 74 V 5.2 La doped BFO 76 5.3 Ru doped BFO 84 5.4 La, Ru codoped BiFeO3 93 5.5 Pb(Zr0.52Ti0.48)O3 (PZT) codoped BFO 101 5.6 Conclusions 110 Chapter Leakage mechanisms of BFO 113 6.1 Introduction 113 6.2 Deposition temperature dependent leakage mechanism 115 6.3 Oxygen pressure dependent leakage mechanism 119 6.4 Leakage mechanism in La and Ru codoped BFO 123 6.5 Conclusions 130 Chapter EPR study of BFO 132 7.1 Introduction 132 7.2 EPR study of pure BFO 134 Chapter Conclusions and Future work 143 8.1 Conclusions 143 8.2 Future Work 145 Reference 146 VI Abstract Magnetoelectric multiferroics exhibit coexisting magnetic and ferroelectric phases, with coupling between magnetic and electric ordering In this work, pulsed laser deposition (PLD) technology has been used to deposit multiferroic pure and chemically modified BiFeO3 (BFO) thin film on different substrates The novelty of our work is to present a systematically of chemically modified BFO thin films combining with the macroscopic and microscopic ferroelectric properties and local domain switching behavior The microstructures, electrical and magnetic properties of the as-grown films are systematically investigated A, B-site and A, B codoped effects have been determined, suggesting that the dopants could greatly impact the multiferroic properties of BFO films In addition, the leakage mechanism of the multiferroic films have been studied at different growth conditions and different measurement conditions, such as temperature and electric field Furthermore, defect chemistry and low temperature magnetic phase transition have been evaluated via electron paramagnetic resonance (EPR) VII List of Tables Table 3.1 Deposition parameter for thin films………………………………… 32 Table 4.1 eff The orientation dependence of d33, Ps, and effective coefficient, Q33 43 Table 7.2 Spin counting for the samples annealed in different atmospheres… 136 VIII List of Figures Figure 2.1 Phase control in ferroic and multiferroics………………………………6 Figure 2.2 The relationship between multiferroic and magnetoelectric………… Figure 2.3 Schematic of the crystal structure of BFO and the ferroelectric polarization (arrow) and antiferromagnetic plane (shaded planes)… 12 Figure 2.4 Polarization of BiFeO3: (a) bulk single crystal and (b) epitaxial thin film…………………………………………………………………….13 Figure 2.5 Schematics of the 64 nm antiferromagnetic circular cycloid The canted antiferromagnetic spins (blue and green arrows) give rise to a net magnetic moment (purple arrows) that is specially averaged out to zero due to the cycloidal rotation The spins are contained within the plane defined by the polarization vector…………………………………….14 Figure 2.6 Schematics of the planes of spin rotations and cycloids k~1 vector for the two polarization domains separated by a domain wall (in light gray) Rotating the polarization by 71o results in a change of the magnetic easy plane, meaning that sublattice magnetization can be switched by an applied voltage……………………………………………………… 16 Figure 2.7 Schematic of the three types of ferroelectric domain walls The ferroelectric polarization (bold arrows) and antiferromagnetic plane (shaded planes)……………………………………………………… 17 Figure 2.8 MERAMs based on exchange-bias coupling between a multiferroic that is ferroelectric and antiferromagnetic (FE-AFM, green layer), and a thin ferromagnetic electrode (blue layer) A tunneling barrier layer between the two top ferromagnetic layers provides the two resistive states……19 Figure 2.9 The variation of photocurrent with sample rotation under illumination with a linearly polarized light The experimental sketch is shown in the inset The PV effect becomes maximum when the polarized-light electric field is parallel to the in-plane component of the ferroelectric polarization and minimum when the field is perpendicular to the inplane component ……………………………………… ………….20 Figure 2.10 Schematic of the pulsed laser deposition system…… ……………… 21 Figure 2.11 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