NANOSCIENCE AND TECHNOLOGY
Springer-Verlag Berlin Heidelberg GmbH
NANOSCIENCE AND TECHNOLOGY
Series Editors: P. Avouris K. von Klitzing H. Sakaki R. Wiesendanger
The series NanoScience and Technology is focused on the fascinating nano-world, mesoscopic physics, analysis with atomic resolution, nano and quantum-effect devices, nanomechanics and atomic-scale processes. All the basic aspects and technology-oriented developments in this emerging discipline are covered by comprehensive and timely books. The series constitutes a survey of the relevant special topics, which are presented by leading experts in the field. These books will appeal to researchers, engineers, and advanced students.
Sliding Friction Physical Principles and Applications By B.N.J. Persson 2nd Edition
Scanning Probe Microscopy Analytical Methods Editor: R. Wiesendanger
Mesoscopic Physics and Electronics Editors: T. Ando, Y. Arakawa, K. Furuya, S. Komiyama, H. Nakashima
Biological Micro- and Nanotribology Nature's Solutions By M. Scherge and S.N. Gorb
Semiconductor Spintronics and Quantum Computation Editors: D.D. Awschalom, N. Samarth, D. Loss
Semiconductor Quantum Dots Physics, Spectroscopy and Applications Editors: Y. Masumoto and T. Takagahara
Nano-Optoelectonics Concepts, Physics and Devices Editor: M. Grundmann
Noncontact Atomic Force Microscopy Editors: S. Morita, R. Wiesendanger, E. Meyer
Nanoelectrodynamics Electrons and Electromagnetic Fields in Nanometer-Scale Structures Editor: H. Nejo
Single Organic Nanoparticles Editors: H. Masuhara, H. Nakanishi, K. Sasaki
Epitaxy of Nanostructures ByV.A. Shchukin, N.N. Ledentsov, D. Bimberg
Nanoscale Characterisation of Ferroelectric Materials Scanning Probe Microscopy Approach Editors: M. Alexe and A. Gruverman
M. Alexe A. Gruverman (Eds.)
Nanoscale Characterisation of Ferroelectric Materials Scanning Probe Microscopy Approach
With 166 Figures
Springer
Dr. Marin Alexe
Max Planck Institute of Microstructure Physics Weinberg 2, 06120 Halle (Saale), Germany E-mail: [email protected]
Series Editors: Professor Dr. Phaedon Avouris
Dr. Alexei Gruverman North Carolina State University, Department of Materials Science and Engineering Campus Box 7920, Raleigh, NC 27695, USA E-mail: [email protected]
IBM Research Division, Nanometer Scale Science & Technology Thomas J. Watson Research Center, P.O. Box 218 Yorktown Heights, NY 10598, USA
Professor Dr., Dres. h.c. Klaus von Klitzing Max-Planck-Institut fur Festkorperforschung, Heisenbergstrasse 1
70569 Stuttgart, Germany
Professor Hiroyuki Sakaki University of Tokyo, Institute ofIndustrial Science, 4-6-1 Komaba, Meguro-ku Tokyo 153-8505, Japan
Professor Dr. Roland Wiesen danger Institut fur Angewandte Physik, Universitiit Hamburg, Jungiusstrasse 11
20355 Hamburg, Germany
Cover picture: Ferroelectric domains in 500 nm lateral size PZT structures, by courtesy of Catalin Harnagea.
ISSN 1434-4904 ISBN 978-3-642-05844-8
Library of Congress Cataloging-in-Publication Data.
Nanoscale characterisation of ferroelectric materials: scanning probe microscopy approach 1 M. Alexe, A. Gruverman, Eds. p. cm. - - (Nanoscience and technology) Includes bibliographical references and index.
ISBN 978-3-642-05844-8 ISBN 978-3-662-08901-9 (eBook) DOI 10.1007/978-3-662-08901-9 1. Nanostructured materials. 2. Nanotechnology. I. Alexe, M. (Marin) II. Gruverman, A. (Alexei) TA418·9·N35N3445 2004 620'.5- -dc22 2004040666
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Preface
Among the main trends in our daily society is a drive for smaller, faster, cheaper, smarter computers with ever-increasing memories. To sustain this drive the computer industry is turning to nanotechnology as a source of new processes and functional materials, which can be used in high-performance high-density electronic systems. Researchers and engineers have been focusing on ferroelectric materials for a long time due to their unique combination of physical properties. The ability of ferroelectrics to transform electromagnetic, thermal, and mechanical energy into electrical charge has been used in a number of electronic applications, most recently in nonvolatile computer memories. Classical monographs, such as Ferroelectricity by E. Fatuzzo and W. J. Mertz, served as a comprehensive introduction into the field for several generations of scientists. However, to meet the challenges of the "nano-era", a solid knowledge of the ferroelectric properties at the nanoscale needs to be acquired. While the science of ferroelectrics from micro- to larger scale is well established, the science of nanoscale ferroelectrics is still terra incognita. The properties of materials at the nanoscale show strong size dependence, which makes it imperative to perform reliable characterization at this size range.
One of the most promising approaches is based on the use of scanning probe microscopy (SPM) which has revolutionized materials research over the last decade. SPM provides a unique opportunity to measure local properties of the matter, to tailor and engineer these properties and to characterize nanoscale devices while operating in ambient forbidden to traditional vacuum-based high-resolution techniques.
The aim of this book is to present recent advances in nanoscale characterization of electrical, mechanical and optical properties of ferroelectric materials made possible due to the use of the SPM techniques. As the field is not mature enough, this book is rather a collection of reviews written by the leading researchers in the field and not a textbook in a traditional sense. Along with the generally accepted concepts there are some new challenging ideas and experimental controversies reflected in the contributions. We hope that this book will make the readers aware of the tremendous developments in the field of nanoscale investigation of ferroelectric materials over the last decade. We also hope that it will inspire further scientific endeavors and will attract students and researchers from diverse disciplines such as chemistry, biology, material science, and electrical engineering.
The first five chapters address fundamentals of SPM methods used in nanoscale investigation of ferroelectrics, the first chapter presents a review of two of the most common SPM techniques used for ferroelectric imaging, electrostatic force
VI Preface
microscopy (EFM) and piezoresponse force microscopy (PFM), analyzing domain contrast formation mechanism in PFM and relative magnitudes of electrostatic versus electromechanical contributions. The second chapter discusses in depth quantitative information about ferroelectric polarization by PFM. Chapter 3 focuses on direct electrical measurements of nanoscale ferroelectrics and chapter 6 presents applications of near-field scanning optical microscopy (NSOM) to probe optical of ferroelectrics at the nanoscale, begins after an overview of conventional optical microscopy techniques for characterization of ferroelectrics. Finally, chapter 5 includes the theory of polarization detection based on nonlinear dielectric response and reports the results of the imaging of the ferroelectric domains using scanning nonlinear dielectric microscopy (SNDM) as well as application of SNDM as a tool for high-density data storage with a density in the terabit range.
The next four chapters present remarkable applications of SPM methods in nanoscale characterizations of ferroelectrics. Chapter 6 shows one of the most successful application of PFM which was used along with a Ginzburg-LandauDevonshire phenomenological theory to explain the dependence of longitudinal piezoelectric constant measured by PFM on the lateral size of nanoscale capacitors fabricated by focused ion beam milling. SPM studies of phase transitions in ferroelectric crystals via observation of domain structure evolution along with the dynamics of domain growth under the tip and local domain switching and hysteresis loop measurements are discussed in Chap. 7. Chapter 8 describes the nanodomain engineering in ferroelectric crystals using high voltage SPM. It presents a comprehensive experimental and theoretical description of a newly discovered effect of domain breakdown: domain growth under practically zero electric field in the crystal bulk. Issues related to nanodomain engineering, such as domain scaling, stability and writing speed, are also discussed. Chapter 9 applies a combination of scanning probe methods to investigate the local dielectric and polarization properties of the PZT film interfaces.
This book is intended to be useful for the undergraduate and graduate students interested in the SPM techniques, electrical engineering, materials science and information technology. Scientists at research centers, industrial engineers, specialists from the SPM community who wish to broaden their knowledge on the development in the related fields may also find this book practical.
We would like to thank our colleagues allover the world who contributed in many ways to the development of nanoscale science of ferroelectrics and particularly the contributing authors of this book.
Halle and Raleigh, January 2004
Marin Alexe Alexei Gruverman
Contents
1 Electric Scanning Probe Imaging and Modification of Ferroelectric Surfaces S. V. Kalinin and D. A. Bonnell .......................................................................... 1
1.1 SPM Imaging and Control of Ferroelectric Materials ..................... 1 1.2 Non-contact Electrostatic Imaging of Ferroelectric Surfaces ......... 3 1.3 Contact Imaging and Polarization Dynamics ............................... 11 1.4 Simultaneous Acquisition of PPM and Potential Images ............. 37 1.5 Conclusions ................................................................................ 39
2 Challenges in the Analysis of the Local Piezoelectric Response C. Harnagea and A. Pignolet ............................................................................. 45
2.1 Introduction ................................................................................ 45 2.2 Analysis of the First Harmonic Signal
in Voltage Modulated SPM ........................................................ .47 2.3 Calibration of the Piezoresponse Signal ...................................... 51 2.4 Local Measurements ................................................................... 53 2.5 Interpretation of the Piezoresponse SignaL ................................ 55 2.6 Electric Field in the Sample ........................................................ 66 2.7 Influence of the Cantilever Elastic Properties
and of the AC Probing Frequency on the Measurements .............. 77 2.8 Conclusions ................................................................................ 81
3 Electrical Characterization of Nanoscale Ferroelectric Structures S. Tiedke and T. Schmitz ................................................................................... 87
3.1 Introduction ................................................................................ 87 3.2 P(V) Curve and Characteristic Values ......................................... 88 3.3 Sample Preparation and Contacting ............................................. 89 3.4 Suitable Measurement Methods .................................................. 92 3.5 Measurement Results and Interpretation ...................................... 98 3.6 Application to Memory Structures ............................................ 108
4 Nanoscale Optical Probes of Ferroelectric Materials J. Levy and O. Tikhomirov .............................................................................. 115
4.1 Introduction .............................................................................. 115 4.2 Overview of Optical Microscopy .............................................. 115 4.3 History of Optical Probes of Ferroelectrics ................................ 118 4.4 Laser Techniques ..................................................................... 120
vm Contents
4.5 Ferroelectric Physics from Optical Probes ................................. 121 4.6 Confocal Scanning Optical Microscopy .................................... 125 4.7 Near-Field Scanning Optical Microscopy .................................. 133 4.8 Future Directions ...................................................................... 137
5 Scanning Nonlinear Dielectric Microscopy for Investigation of Ferroelectric Polarization Y. Cho ............................................................................................................ 143
5.1 Introduction ............................................................................. 143 5.2 Principle and Theory for SNDM ............................................... 144 5.3 Higher Order Nonlinear Dielectric Microscopy ......................... 149 5.4 Three-Dimensional Measurement Technique ............................ 153 5.5 Tbit/inch2 Ferroelectric Data Storage Based on SNDM ............. 155 5.6 Conclusions ............................................................................. 161
6 Nanoscale Piezoelectric Phenomena in Epitaxial PZT Thin Films V. Nagarajan, A. Roytburd, and R. Ramesh ..................................................... 163
6.1 Introduction ............................................................................. 163 6.2 Nonlinear Thermodynamic Theory ........................................... 165 6.3 What Happens in Small Confined Dimensions?
(Piezoelectric Measurements On Nanoscale Islands) ................. 172 6.4 Conclusions ............................................................................. 189
7 Scanning Probe Microscopy of Ferroelectric Domains near Phase Transitions M. Abplanalp, M. Zgonik, and P. Giinter ......................................................... 193
7.1 Introduction ............................................................................. 193 7.2 Piezoresponse Scanning Force Microscopy ............................... 195 7.3 Ferroelectric Domains near Phase Transitions ........................... 201 7.4 Local Hysteresis Loops and Nanoscale Switching
of Domains .............................................................................. 210 7.5 Conclusions ............................................................................. 218
8 Nanodomain Engineering in Ferroelectric Crystals Using ffigh Voltage Atomic Force Microscopy Y. Rosenwaks, M. Molotskii, A. Agronin, P. Urenski, M. Shvebelman, and G. Rosenman ............................................................................................ 221
8.1 Introduction ............................................................................. 221 8.2 Nanodomain Reversal in Ferroelectric Crystals
Using High Voltage Atomic Force Microscopy ......................... 229 8.3 Piezoelectric Coefficient Measurements
Using High Voltage Atomic Force Microscopy ......................... 246 8.4 Nanodomain Characterization
Using Scanning Probe Microscopy ........................................... 250 8.5 Summary and Conclusions ....................................................... 261
Contents IX
9 Nanoinspection of Dielectric and Polarization Properties at Inner and Outer Interfaces in PZT Thin Films L.M. Eng, S. Grafstrom, C. Loppacher, X.M. Lu, F. Schlaphof, K. Franke, G. Suchaneck, and G. Gerlach ........................................................ 267
9.1 Introduction .............................................................................. 267 9.2 Methods ................................................................................... 268 9.3 Materials .................................................................................. 270 9.4 Results ..................................................................................... 271 9.5 Conclusions .............................................................................. 276
Index .............................................................................................................. 279
List of Contributors
Abplanalp, Markus ABB Switzerland Ltd. Corporate Research Electro-Technologies BadenDaettwil, Switzerland
Agronin, Alex Department of Electrical Engineering-Physical Electronics, Tel Aviv University Ramat Aviv, 69978 Tel Aviv, Israel
Bonnell, Dawn A. University of Pennsylvania Philadelphia, PA 19104 USA
Cho, Yasuo Research Institute of Electrical Communication, Tohoku University 2-1-1 Katahira, Aoba-ku, Sendai 980-8577 Japan
Eng, Lukas M. Institute of Applied Photophysics, TUDresden D-01062 Dresden Germany
Franke, Kurt Institut fur Festk6rper- und Werkstoffforschung Dresden e.V., D-O 1 069 Dresden Germany
Gerlach, Gerald Institute of Solid State Electronics, TUDresden D-01062 Dresden Germany
Grafstrom, Stefan Institute of Applied Photophysics, TUDresden D-01062 Dresden Germany
GUnter, Peter Nonlinear Optics Laboratory, Institute of Quantum Electronics Swiss Federal Institute of Technology (ETH), Ziirich, Switzerland
Harnagea, Catalin INRS - Energie, Materiaux & Telecommunications 1650, boulevard Lionel-Boulet, Varennes (Quebec) J3X IS2 Canada
Kalinin, Sergei V. Condensed Matter Sciences Division, Oak Ridge National Laboratory Oak Ridge, TN 37831 USA
XU List of Contributors
Levy, Jeremy Department of Physics and Astronomy, University of Pittsburgh 3941 O'Hara St., Pittsburgh, PA 15260 USA
Loppacher, Christian Institute of Applied Photophysics, TUDresden D-O 1062 Dresden Germany
Lu, XiaoMei Institute of Applied Photophysics, TUDresden D-O 1062 Dresden Germany and Physics Department, Nanjing University Nanjing 210008, P. R. China
Molotskii, Michel The Wolfson Materials Research Center Tel Aviv University, Ramat-Aviv, 69978 Israel
Nagarajan, Valanoor Materials Research Science and Engineering Center University of Maryland College Park, MD 20742 USA
Pignolet, Alain INRS - Energie, Materiaux & Telecommunications 1650, boulevard Lionel-Boulet, Varennes (Quebec) J3X IS2 Canada
Ramesh, Ramamurthy Materials Research Science and Engineering Center University of Maryland College Park, MD 20742 USA
Rosenman, Gil Department of Electrical Engineering-Physical Electronics, Tel Aviv University Ramat Aviv, 69978 Tel Aviv, Israel
Rosenwaks, Yossi Department of Electrical Engineering-Physical Electronics, Tel Aviv University Ramat Aviv, 69978 Tel Aviv, Israel
Roytburd, Alexander , Materials Research Science and Engineering Center University of Maryland College Park, MD 20742 USA
Schlaphof, Frank Institute of Applied Photophysics, TUDresden D-O 1062 Dresden Germany
Schmitz, Thorsten aixACCT Systems GmbH Dennewartstr. 25-27 D-52068 Aachen, Germany
Shvebelman, Maria Department of Electrical Engineering -Ph ysical Electronics, Tel Aviv University Ramat Aviv, 69978 Tel Aviv, Israel
Suchaueck, Gunnar Institute of Solid State Electronics, TUDresden, D-O 1062 Dresden, Germany
Tiedke, Stephan aixACCT Systems GmbH Dennewartstr. 25-27 D-52068 Aachen, Germany
Tikhomirov, Oleg Institute of Solid State Physics Chernogolovka, 142432 Russia
List of Contributors XIII
Urenski, Pavel Department of Electrical Engineering-Physical Electronics, Tel Aviv University Ramat Aviv, 69978 Tel Aviv, Israel
Zgonik, Marko Dept. of Physics, University of Ljubljana and J. Stefan Institute Ljubljana Slovenia