Gruverman Scanning Probe Microscopy of Functional Materials

Nanoscale Imaging and Spectroscopy
1. Auflage 2010
ISBN: 978-1-4419-7167-8
Verlag: Springer-Verlag
Format: PDF
Kopierschutz: Adobe DRM (»Systemvoraussetzungen)

E-Book, Englisch, 555 Seiten

The goal of this book is to provide a general overview of the rapidly developing field of novel scanning probe microscopy (SPM) techniques for characterization of a wide range of functional materials, including complex oxides, biopolymers, and semiconductors. Many recent advances in condensed matter physics and materials science, including transport mechanisms in carbon nanostructures and the role of disorder on high temperature superconductivity, would have been impossible without SPM. The unique aspect of SPM is its potential for imaging functional properties of materials as opposed to structural characterization by electron microscopy. Examples include electrical transport and magnetic, optical, and electromechanical properties. By bringing together critical reviews by leading researchers on the application of SPM to to the nanoscale characterization of functional materials properties, this book provides insight into fundamental and technological advances and future trends in key areas of nanoscience and nanotechnology.

Sergei Kalinin is a researcher at Oak Ridge National Laboratory. Alexei Gruverman is an associate professor at University of Nebraska-Lincoln.

Autoren/Hrsg.

Gruverman, Alexei

Inhaltsverzeichnis

1;Preface;6
1.1;References;10
2;Contents;12
3;Contributors;16
4;Part I:Spectroscopic SPM at theResolution Limits;20
4.1;Chapter 1: Excitation and Mechanisms of Single Molecule Reactions in Scanning Tunneling Microscopy;21
4.1.1;Introduction;21
4.1.2;Measurement of Single-Molecule Reactions;23
4.1.3;Excitation Rate;24
4.1.4;Energy Threshold for a Vibrationally Mediated Reactions and Action Spectroscopy;26
4.1.5;Reactions Involving Excited Electronic and Anionic States;30
4.1.6;Rate Constant of a Single-Molecule Reaction;33
4.1.7;Theoretical Aspects of Single- and Multiple-Electron Processes;34
4.1.8;Delocalized Excitation in the Molecular Junction;40
4.1.9;Tip Effects and Field-Induced Manipulation;44
4.1.10;Collective Reactivity of Molecular Aggregates;46
4.1.11;Conclusions and Outlook;50
4.1.12;References;50
4.2;Chapter 2: High-Resolution Architecture and Structural Dynamics of Microbial and Cellular Systems: Insights from in Vitro Atomic Force Microscopy;56
4.2.1;Introduction;56
4.2.2;AFM Investigations of Spore Morphology, Structural Dynamics and Spore Coat Architecture;57
4.2.2.1;Bacillus and Clostridium Spore Morphology;58
4.2.2.2;Spore Size Distributions;60
4.2.2.3;Spore Response to a Change in the Environment from Fully Hydrated to Air-Dried State;61
4.2.2.4;High-Resolution Structure and Assembly of the Spore Coat;63
4.2.2.5;Unraveling of the Spore Coat Assembly with AFM-Based Immunolabeling;69
4.2.2.6;Spore Coat Assembly;71
4.2.3;Mechanisms of Spore Germination;72
4.2.3.1;Emergence of Vegetative Cells;76
4.2.3.2;Bacteria–Mineral Interactions on the Surfaces of Metal-Resistant Bacteria;81
4.2.4;References;83
5;Part II:Dynamic Spectroscopic SPM;86
5.1;Chapter 3: Dynamic Force Microscopy and Spectroscopy in Ambient Conditions: Theory and Applications;87
5.1.1;Introduction;87
5.1.2;General Theory of Dynamic Force Microscopy;88
5.1.2.1;Formulation of the Problem and Basic Equation of Motion;88
5.1.2.2;Driven and Self-Driven Cantilevers in Dynamic Force Microscopy;91
5.1.2.3;Tip–Sample Interaction Force in Air;93
5.1.2.4;Theory of AM Mode Including Tip–Sample Forces;94
5.1.2.5;Measuring the Tip–Sample Interaction Force;98
5.1.2.6;Theory of FM Mode Including Tip–Sample Forces;101
5.1.3;Mapping of Tip–Sample Interactions in Ambient Conditions;103
5.1.3.1;Experimental Comparison of the AM- and FM mode;103
5.1.3.2;Mapping the Tip–Sample Interactions on Biological Samples;105
5.1.4;Conclusion;107
5.1.5;Acknowledgments;108
5.1.6;References;108
5.2;Chapter 4: Measuring Mechanical Properties on the Nanoscale with Contact Resonance Force Microscopy Methods*;111
5.2.1;Introduction;111
5.2.2;Single-Point Measurements of Elastic Modulus;113
5.2.2.1;Basic Concepts;113
5.2.2.2;Models for Data Analysis;114
5.2.2.3;Experimental Techniques;117
5.2.2.4;Results for Elastic Modulus;119
5.2.3;Beyond the Basics: Further CR-FM Techniques;120
5.2.3.1;Measuring Shear Elastic Properties;120
5.2.3.2;Measuring Viscoelastic Properties;123
5.2.4;Imaging with CR-FM Techniques;127
5.2.4.1;Qualitative Stiffness Imaging;127
5.2.4.2;Quantitative Imaging: Modulus Mapping;128
5.2.4.3;Application to Buried Interfaces;133
5.2.5;Summary and Conclusions;136
5.2.6;References;137
5.3;Chapter 5: Multi-Frequency Atomic Force Microscopy;141
5.3.1;Multi-Frequency Motivation;142
5.3.2;Cantilever Resonant Modes and Boundary Conditions;143
5.3.3;Methods;147
5.3.4;Attractive and Repulsive Mode;147
5.3.5;Feedback;148
5.3.6;Intermittent- and Non-contact Bimodal Experimental Results;149
5.3.7;The Energy Viewpoint;151
5.3.8;High Resolution, Low Force Bimodal Imaging;154
5.3.9;Separating Long- and Short-Range Forces: Bimodal Magnetic Force Microscopy;156
5.3.10;Multiple Frequencies at the Same Resonance Peak;156
5.3.10.1;Revisiting Past Assumptions: More Than Two Independent Variables;156
5.3.11;Frequency Tracking;158
5.3.12;Dual AC Resonance Tracking;159
5.3.13;Intermodulation AFM;162
5.3.14;Conclusions, Future Challenges and Opportunities;163
5.3.15;References;164
5.4;Chapter 6: Dynamic Nanomechanical Characterization Using Multiple-Frequency Method;168
5.4.1;Measurement Basics;169
5.4.1.1;The Tapping Cantilever Moves in a Sinusoidal Trajectory;170
5.4.1.2;Information About the Mechanical Properties Are Contained in Higher Harmonic Forces;171
5.4.1.3;There Are Multiple Force Sensors in a Single Cantilever;174
5.4.2;High-Speed and High Spatial Resolution Nanomechanical Analysis with Large Dynamic Range;181
5.4.2.1;Torsional Harmonics Provide a Large Dynamic Range in Mechanical Measurements;181
5.4.2.2;High Resolution Maps of Stiffness, Adhesion, and Dissipation Can Be Obtained in a Single Tapping-Mode Scan;184
5.4.2.3;Sub-molecular Resolution Mechanical Measurements with Ultra Sharp Tips and Lower Forces;187
5.4.2.4;High Resolution Thermo-Mechanical Characterization of Polymer Blends;189
5.4.3;References;193
6;Part III:Thermal Characterization by SPM;194
6.1;Chapter 7: Toward Nanoscale Chemical Imaging: The Intersection of Scanning Probe Microscopy and Mass Spectrometry;195
6.1.1;Introduction;195
6.1.2;Atmospheric Pressure Mass Spectrometry Techniques;198
6.1.2.1;Thermal Desorption with Secondary Ionization Mass Spectrometry;198
6.1.2.2;Laser Desorption (Ablation) Ionization Mass Spectrometry;200
6.1.3;References;209
6.2;Chapter 8: Dynamic SPM Methods for Local Analysis of Thermo-Mechanical Properties;213
6.2.1;The Need for Localized Mechanical Analysis: Industrial and Basic Science Perspective;213
6.2.2;Mechanical Characterization of the Materials with High Spatial Resolution: Lessons from Nanoindentation;214
6.2.3;Principles of Thermo-Mechanical Analysis Using AFM Platform: Examples of Thermo-Mechanical Properties Mapping;216
6.2.3.1;Transition Temperature Microscopy;217
6.2.3.2;Scanning Thermal Expansion Microscopy;220
6.2.3.3;Thermally Assisted Atomic Force Acoustic Microscopy;222
6.2.3.4;Multiple Frequency Methods for Thermo-Mechanical Mapping (BE-NanoTA and Z-Therm);223
6.2.4;Types of Probes Used for Thermo-Mechanical Analysis;231
6.2.4.1;Wollaston Probe;231
6.2.4.2;Silicon Heater;233
6.2.5;Mathematical Models for Understanding Thermo-Mechanical Results;234
6.2.5.1;Contact Mechanics Model of Elastic Media in the Presence of a Heat Transfer;235
6.2.5.2;Contact Mechanical Model for Deconvolution of the Mechanical Properties of Samples from Parameters of Tip–Surface Contact Resonance;236
6.2.6;Technique Development Prospects and Limitations;237
6.2.7;References;240
7;Part IV:Electrical and Electromechanical SPM;244
7.1;Chapter 9: Advancing Characterization of Materials with Atomic Force Microscopy-Based Electric Techniques;245
7.1.1;Scanning Probe Microscopy in its Development;245
7.1.2;Electrostatic and Electromechanical Interactions in Atomic Force Microscopy;248
7.1.2.1;Detection of Electrostatic Responses in AFM;250
7.1.2.2;KFM Applications;252
7.1.2.3;Challenges and Solutions;255
7.1.2.4;Piezoresponse Force Microscopy: Background and Applications;257
7.1.3;Implementation of EFM, KFM and PFM;262
7.1.3.1;Electric Force Microscopy and Kelvin Force Microscopy: AM–AM approach;262
7.1.3.2;Electric Force Microscopy and Kelvin Force Microscopy: AM–FM Approach;265
7.1.3.3;Experiments in PFM;267
7.1.3.4;Probes for AFM-Based Electric Studies;270
7.1.4;Practical Studies with AFM-Based Electric Modes;273
7.1.4.1;General Comments;273
7.1.4.2;Evaluation of Different Approaches in EFM and KFM;280
7.1.4.3;Metals and Semiconductors;288
7.1.4.4;Examination of Molecular Self-Assemblies;293
7.1.5;Conclusions and Further Outlook;306
7.1.6;References;308
7.2;Chapter 10: Quantitative Piezoresponse Force Microscopy: Calibrated Experiments, Analytical Theory and Finite Element Modeling;313
7.2.1;Ferroelectric Wall Width as a PFM Challenge;314
7.2.2;Calibration, Background Subtraction, and Frequency Dispersion of PFM Displacements;317
7.2.3;Tip Size Dependence of PFM Amplitude and Profile;318
7.2.4;Finite Element Simulation: General Approach;322
7.2.5;FEM Simulation of the Potential and Electric Fields Under the PFM Tip;323
7.2.6;Comparison Between Vertical PFM Experiments, Simulation, and Theory;330
7.2.7;Lateral PFM: Experiments, Simulation, and Theory;334
7.2.8;Conclusions;337
7.2.9;References;338
7.3;Chapter 11: High-Speed Piezo Force Microscopy: Novel Observations of Ferroelectric Domain Poling, Nucleation, and Growth;341
7.3.1;Introduction;341
7.3.2;High-Speed Piezo Force Microscopy;342
7.3.3;High-Speed Imaging;344
7.3.4;Domain Wall Motion;346
7.3.5;Domain Nucleation and Growth;348
7.3.6;High-Speed Domain Writing;352
7.3.7;Other Applications;354
7.3.8;Conclusion;355
7.3.9;References;355
7.4;Chapter 12: Polar Structures in Relaxors by Piezoresponse Force Microscopy;357
7.4.1;Introduction;357
7.4.2;Polar Nanoregions: Experimental Evidences, Structure, Mechanisms;358
7.4.3;Temperature Evolution of Polar Structures in Relaxors;360
7.4.4;Piezoresponse Force Microscopy Investigations of Uniaxial Relaxors SrxBa1–xNb2O6;363
7.4.4.1;SrxBa1–xNb2O6: Structural Considerations;363
7.4.4.2;SrxBa1–xNb2O6: Polar Structures Below TC;365
7.4.4.3;SrxBa1–xNb2O6: Temperature Evolution of the Polar Structures;370
7.4.5;Piezoresponse Force Microscopy Studies of Cubic Relaxors;374
7.4.5.1;Pb(Mg1/3Nb2/3)O3–PbTiO3 Single Crystals;374
7.4.5.2;PbZn1/3Nb2/3O3–PbTiO3 Single Crystals;379
7.4.6;Polycrystalline Materials (Ceramics);383
7.4.6.1;Temperature Evolution of Domains in the PMN–PT Ceramics;383
7.4.6.2;Grain Size Effect in Pb0.9125La0.0975(Zr0.65Ti0.3)0.976O3 Ceramics;385
7.4.7;Thin Films;388
7.4.8;Outlook;391
7.4.9;References;392
7.5;Chapter 13: Symmetries in Piezoresponse Force Microscopy;396
7.5.1;Conventional Interpretation of PFM Images;396
7.5.1.1;Orientation of the Polarization and the Piezoelectric Tensor;397
7.5.1.2;Nonlocal Piezoelectric Response;398
7.5.2;Device Asymmetries;399
7.5.2.1;Cantilever Axes: Optical Amplification;400
7.5.2.2;Deconvolution of Cantilever Deflection Modes:Mechanical Crosstalk;401
7.5.2.3;Alignment of the Photodiode: Optical Crosstalk;403
7.5.2.4;Beam Asymmetry;405
7.5.3;Sample Asymmetries;405
7.5.3.1;Topography;405
7.5.3.1.1;Induced Topography;406
7.5.3.1.2;Topography Crosstalk;408
7.5.3.2;Local Heterogeneities;408
7.5.3.3;Substrate Signatures;410
7.5.3.4;Conductivity;411
7.5.4;Contact Asymmetries;411
7.5.4.1;Tip Curvature;411
7.5.4.2;Bow Waves;412
7.5.5;Summary;412
7.5.6;References;413
8;Part V:Novel SPM Concepts;414
8.1;Chapter 14: New Capabilities at the Interface of X-Rays and Scanning Tunneling Microscopy*;415
8.1.1;Introduction;415
8.1.2;Basic Interactions of X-Rays with Matter;416
8.1.3;The Physics of X-Ray-Enhanced Scanning Tunneling Microscopy;419
8.1.4;The Development of Synchrotron Radiation-EnhancedScanning Tunneling Microscopy;423
8.1.5;Fabrication of Insulator-Coated Smart Tips;427
8.1.6;Photoelectron Detection Using a Scanning Tunneling Microscope;429
8.1.7;X-Ray-Assisted Scanning Tunneling Microscopy;435
8.1.8;Concluding Remarks;439
8.1.9;References;440
8.2;Chapter 15: Scanning Ion Conductance Microscopy;442
8.2.1;Introduction;442
8.2.2;Fundamental Principles;443
8.2.2.1;Basic Experimental Setup;443
8.2.2.2;Nanopipette Probes;444
8.2.2.3;Half-Cell Electrodes;445
8.2.2.4;Ionic Conductivity;446
8.2.3;Ionic Currents in SICM;447
8.2.3.1;Geometry of the Pipette–Sample System;447
8.2.3.2;Analytical Model;448
8.2.3.3;Finite Element Model;449
8.2.3.4;Experimental Ion Current vs. Distance Curves;451
8.2.4;Basic Imaging Modes;452
8.2.4.1;Imaging with Simple Ion Current Feedback;452
8.2.4.2;Limitations of Simple Ion Current Feedback;454
8.2.4.3;Distance-Modulation Methods;455
8.2.4.4;Applications;456
8.2.5;Advanced Imaging Modes;459
8.2.5.1;High-Resolution Imaging;459
8.2.5.2;Combination with Other Scanning Techniques;460
8.2.5.2.1;Combination with Optical Microscopy;461
8.2.5.2.2;Combination with Atomic Force Microscopy;461
8.2.5.2.3;Combination with Shear Force Microscopy;462
8.2.5.3;Elasticity Measurements with SICM;464
8.2.6;Outlook;466
8.2.7;References;466
8.3;Chapter 16: Combined Voltage-Clamp and Atomic Force Microscope for the Study of Membrane Electromechanics;470
8.3.1;Introduction;470
8.3.1.1;Tools for Membrane Electromechanics at Molecular Scale;470
8.3.2;Background on Voltage-Clamp AFM on Cells;472
8.3.3;Methods;474
8.3.3.1;Channel cDNA;474
8.3.3.2;Cell Culture and Transfection;474
8.3.3.3;Recording Solutions;474
8.3.3.4;Voltage Cl475
8.3.3.5;Atomic Force Microscopy;475
8.3.3.6;AFM Cantilevers;475
8.3.3.7;AFM Measurement of Cell Stiffness;476
8.3.3.8;VC-AFM Setup;476
8.3.3.9;VC-AFM Data Acquisition;476
8.3.3.10;Data Selection and Analysis;478
8.3.4;Results;478
8.3.5;Force Cl478
8.3.5.1;Limitations of a Cantilever as a Force Sensor;478
8.3.5.2;Cell is a Mechanically Imperfect Substrate;479
8.3.6;Electrical Behavior of Wild-Type and Shaker-Transfected HEK Cells;483
8.3.6.1;Membrane Electro-Mechanics (MEM);483
8.3.6.1.1;Wild-Type HEK MEM;483
8.3.7;Acetylcholine Receptor Transfected HEK MEM;486
8.3.8;Shaker-Transfected HEK MEM;486
8.3.9;NMDG+Ion Replacement;488
8.3.10;Symmetric K+;490
8.3.11;Shaker IL Mutant MEM;490
8.3.12;Discussion;492
8.3.12.1;Channel Density;493
8.3.12.2;Flux Effects;493
8.3.13;References;496
8.4;Chapter 17: Dynamic and Spectroscopic Modes and Multivariate Data Analysis in Piezoresponse Force Microscopy;499
8.4.1;Introduction;499
8.4.1.1;Electromechanics on the Nanoscale;499
8.4.1.2;Piezoresponse Force Microscopy;501
8.4.2;Switching Spectroscopy-PFM;504
8.4.2.1;PFM Spectroscopy;504
8.4.2.2;Switching Spectroscopy-Piezoresponse Force Microscopy of Films;507
8.4.2.3;SS-PFM of Capacitors;512
8.4.3;High-Frequency PFM and Topographic Cross-Talk;516
8.4.3.1;Historical Notes;517
8.4.4;Dual AC Resonance Tracking in PFM;520
8.4.5;Band Excitation PFM;522
8.4.5.1;The Need for Band Excitation;522
8.4.5.2;Principles of Band Excitation;523
8.4.5.3;Data Analysis in Band Excitation;524
8.4.5.3.1;Fitting Models;524
8.4.5.3.2;Principle Component Analysis;526
8.4.6;Band Excitation Piezoresponse Spectroscopy;528
8.4.6.1;BEPS of Free Surfaces;529
8.4.7;Summary and Outlook;532
8.4.8;References;532
8.5;Chapter 18: Polarization Behavior in Thin Film Ferroelectric Capacitors at the Nanoscale;537
8.5.1;Introduction;537
8.5.2;Experimental Approach;538
8.5.3;Capacitor Scaling Effect on Domain Switching Kinetics;541
8.5.4;Effect of Film Microstructure on Domain Switching Kinetics;542
8.5.5;Mechanical Stress Effect on Static Polarization Behavior;544
8.5.6;Summary;547
8.5.7;References;547
9;Index;549