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: malexe@mpi-halle.de

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: AlexeLGruverman@ncsu.edu

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

This work is subject to copyright. All rights are reserved, whether the whole or part of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproduction on microfilm or in any other way, and storage in data banks. Duplication of this publication or parts thereof is permitted only under the provisions of the German Copyright Law of September 9, 1965, in its current version, and permission for use must always be obtained from Springer-Verlag Berlin Heidelberg GmbH. Violations are liable for prosecution under the German Copyright Law.

springeronline.com

© Springer-Verlag Berlin Heidelberg 2004 Originally published by Springer-Verlag Berlin Heidelberg New York in 2004 Softcover reprint of the hardcover 1st edition 2004

The use of general descriptive names, registered names, trademarks, etc. in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use.

Typesetting: Data conversion by the authors using a Springer TEX macro package Final processing by LE-TEX Jelonek, Schmidt & Vockler GbR, Leipzig Cover design: design & production, Heidelberg

Printed on acid-free paper SPIN: 10872085 57/3141/YL - 5 43210

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