SCANNING PROBE MICROSCOPY

AND SPECTROSCOPY Theory, Techniques,

and Applications Second Edition

Edited by

Dawn A. Bonnell

©WILEY-VCH A JOHN WILEY & SONS, INC., PUBLICATION

New York • Chichester • Weinheim • Brisbane • Singapore • Toronto

CONTENTS

Preface ix

Preface to the First Edition xi

Contributors xiii

PART I: FUNDAMENTALS OF OPERATION 1

1 Introduction 3 Dawn A. Bonneil

2 Basic Principles of Scanning Probe Microscopy 7 Dawn A. Bonneil and Bryan D. Huey

2.1 The Local Probe Approach / 8 2.2 Principles of Electron Tunneling / 8 2.3 Principles of Atomic Forces / 14 2.4 System Design / 22 2.5 Data Analysis / 32

3 Theory of Scanning Tunneling Microscopy 43 J. Tersoff

3.1 Introduction / 43 3.2 Theory of STM / 44 3.3 Metal Surfaces: STM as Surface Topography / 48 3.4 Semiconducting Surfaces: Role of Surface

Electronic Structure / 51 3.5 Mechanical Tip-Sample Interactions / 54

VI CONTENTS

4 Methods of Tunneling Spectroscopy with the STM 59 R. J. Hamers and D. F. Padowitz

4.1 Introduction / 60 4.2 Voltage-Dependent STM Imaging / 62 4.3 Modulation Techniques: STS / 73 4.4 Local /- V Measurements / 78 4.5 General Features of Tunneling Spectra / 92 4.6 Other Spectroscopies / 101 4.7 Summary / 106

PART II: TIPS AND SURFACES 111

5 The Surface Structure of Crystalline Solids 113 W. N. Unertl

5.1 Ideal Surfaces of Crystalline Materials / 115 5.2 Thermodynamic Properties of Surfaces / 126 5.3 Defects and the Surfaces of Real Materials / 139 5.4 Traditional Techniques for Surface

Structure Determination / 145 5.5 The Role for STM and AFM / 149

6 The Preparation of Tip and Sample Surfaces for Scanning Probe Experiments 155 Richard L. Smith and Gregory S. Rohr er

6.1 The Preparation of Scanning Tunneling Microscopy Tips / 156

6.2 The Preparation of Scanning Force Microscopy Tips / 172 6.3 Sample Surface Preparation / 182

PART III: APPLICATIONS OF SCANNING PROBE MICROSCOPY 203

7 Electrostatic and Magnetic Force Microscopy 205 Sergei V. Kalinin and Dawn A. Bonneil

7.1 Introduction / 205 7.2 Electrostatic Probe Imaging / 207 7.3 Magnetic Probe Imaging / 230 7.4 Recent Advances in SPM / 245

CONTENTS VÜ

8 BEEM and the Characterization of Buried Interfaces 253 W. J. Kaiser, L. D. Bell, M. H. Hecht and L. C. Davis

8.1 Introduction / 254 8.2 Theory / 257 8.3 Experimental Considerations / 268 8.4 Results / 271 8.5 Recent Applications of BEEM / 284 8.6 Summary / 285

9 The Scanning Probe Microscope in Biology 289 S. M. Lindsay

9.1 Introduction / 290 9.2 Fundamentals of AFM: Sensitivity and Resolution / 291 9.3 Interactions at a Liquid-Solid Interface / 296 9.4 Mechanics of the AFM Cantilever in a Fluid / 301 9.5 Mechanism of Dynamic Force Microscopy

in Fluid / 302 9.6 Practical Instrumentation / 313 9.7 Sample Preparation / 315 9.8 Imaging / 319 9.9 Nonlinear Elasticity of Individual Molecules / 321 9.10 Chemical Bonds and Antibody-Antigen Interactions / 324 9.11 STM Images and Electrical Measurements

on Single Molecules / 326 9.12 Future Developments / 330

10 Nanomechanics 337 Nancy A. Burnham and Richard J. Colton

10.1 Introduction / 338 10.2 Nanomechanics / 339 10.3 Interpreting the Experiment / 355 10.4 Summary / 364

11 Near-Field Scanning Optical Microscopy 371 Daniel A. Higgins and Erwen Mei

11.1 Introduction / 372 11.2 Theory / 375 11.3 Instrumentation / 382 11.4 Emerging NSOM Methods and Applications / 403 11.5 Conclusions / 413

VIII CONTENTS

12 Applications in Electrochemistry Allan J. Bard and Fu-Ren F. Fan

12.1 Apparatus for Electrochemical STM / 422 12.2 Applications of Electrochemical STM / 429 12.3 Scanning Electrochemical Microscopy / 443 12.4 Summary / 447

421

APPENDICES

Appendix I Definitions of Variables

Appendix II Definitions of Acronyms

453

455

459

Appendix III Empiricai Simulation of STM Images: Application to Oxides

Appendix IV Caiculations of Tunneling Current

461

481

Index 487