Preface ........................................................ xi
Authors ...................................................... xiii
Chapter 1 Introduction ......................................... 1
Observing Nature: Sequentiality and Simultaneity ................ 1
Combination Macroscopic/Microscopic: Extending Measurable
Range to Better Understand the Connection
between Ultrastructure and Function .......................... 4
Combination Model-Based/Direct Observation ................... 4
Making the Right Choice ................................... 4
How to Judge the Applicability of a Model ................. 5
Combination Preparative/Measuring Technique .................. 5
Combination of Local Techniques to Track the Dynamics of
Processes .................................................... 6
Combination of Local Techniques of Different Contrast ........ 6
Systems That Can Profit from Combined Techniques ................ 6
Living Cells ................................................. 6
Films ........................................................ 8
Final Remarks ................................................... 8
References ...................................................... 9
Chapter 2 Scanning Probe Microscopy as an Imaging Tool: The
Blind Microscope ............................................... 11
Probe Imaging .................................................. 11
The SPM Family .............................................. 24
The Scanning Probe Microscope ............................... 25
AFM ...................................................... 26
STM ...................................................... 26
Probes and Tips ................................................ 26
STM Probes ............................................... 28
AFM Probes ............................................... 30
Scanners .................................................... 33
Detection of the Tip's Position ............................. 36
Tunneling Detection ...................................... 36
Optical Beam Detection ................................... 37
Piezoresistive Detection ................................. 38
SPM Imaging Modes .............................................. 38
Feedback Mechanism: Controlling the Property X ................. 39
Feedback in Contact Mode ................................. 41
Feedback in Noncontact Mode .............................. 41
Feedback in Intermittent-Contact Mode .................... 43
Topography and More: Feedback on X Mapping Y ................ 44
Artifacts in SPM Images ..................................... 46
Time Resolution in SPM Imaging .............................. 49
Summary ........................................................ 51
References ..................................................... 53
Chapter 3 What Brings Optical Microscopy: The Eyes at the
Microscale ..................................................... 55
Fundamentals of Optical Microscopy ............................. 55
Essential Parts of an Optical Microscope: The Image and
Diffraction Planes ............................................. 64
Diffraction Sets the Limit of Detection, Spatial Resolution,
and Depth of Focus ............................................. 66
Interference Sets Image Formation .............................. 69
Optical Contrasts .............................................. 69
Phase Contrast .............................................. 70
Differential Interference Contrast .......................... 71
Fluorescence Microscopy: Bestowing Specificity ................. 72
Optical Microscopy of Fluorescent Objects ................... 77
Light Source ............................................. 78
Collecting the Emitted Fluorescence: The Dichroic Mirror
and the Emission Filter .................................. 78
Drawbacks of Fluorescence Microscopy: The Ever-Present
Photobleaching .............................................. 80
High-Performance Modes of Fluorescence Microscopy .............. 81
Confocal Laser Scanning Microscopy (CLSM) ................... 81
Fluorescence Lifetime Imaging Microscopy (FLIM) ............. 83
Total Internal Reflection Fluorescence (TIRF): A Near-Field
Microscopy .................................................. 86
TIRF Is Based on the Optical Principles of Total Internal
Reflection ............................................... 86
An Evanescent Wave Acts as the Excitation Source in TIRF . 86
Fluorescence Scanning Near-Field Optical Microscopy
(Fluorescence SNOM) ......................................... 89
More than Near-Field Fluorescence Imaging ................ 93
Photobleaching or Background—Despite Weak and Highly
Localized Illumination ................................... 93
Optical Microscopies: Summary .................................. 95
Combined OM-SPM Techniques: Eyesight to the Blind .............. 95
SPM and Optical Fluorescence Microscopy ..................... 98
Fluorescence SNOM and Single-Molecule Detection ............ 106
Single Fluorescent Molecules as Test Samples ............... 107
Single-Molecule Imaging: Obtaining Molecular Orientations .. 108
Conformations of Single-Polymer Chains in Films ......... 109
Single-Molecule Diffusion ............................... 111
Distribution of Molecules and Molecular Complexes of
Biological Interest in Synthetic and Native Membranes ... 112
References ................................................. 115
Chapter 4 What Brings Scanning Near-Field Optical
Microscopy: The Eyes at the Nanoscale ..................... 119
Fundamentals of Scanning Near-Field Optical Microscopy ........ 119
Background Suppression ..................................... 124
The Nature of the SNOM Probe: Aperture and Apertureless
SNOM ....................................................... 126
Aperture SNOM ........................................... 126
Apertureless SNOM ....................................... 128
The History of SNOM Is the History of Its Probes ........... 131
Aperture Probes ......................................... 132
Apertureless Probes ..................................... 135
Tip-on-Aperture Probes .................................. 135
Feedback Modes in SNOM ..................................... 135
Contrast Mechanisms in SNOM ................................ 137
Polarization Contrast ................................... 140
Refractive Index Contrast ............................... 142
Infrared-Vibrational Contrast (Infrared Apertureless
SNOM) ................................................... 142
Summary .................................................... 142
Applications of SNOM .......................................... 143
References .................................................... 149
Chapter 5 Adding Label-Free Chemical Spectroscopy: Who Is
Who? .......................................................... 153
Chemical Spectroscopy ......................................... 153
Raman (and IR) Microscopy ..................................... 166
Raman Microscopy beyond the Diffraction Limit: Near-Field
Raman Spectroscopy ......................................... 168
Aperture Near-Field Raman Spectroscopy .................. 169
Tip-Enhanced Near-Field Raman Spectroscopy (TERS) ....... 169
Tip-Enhanced Coherent Anti-Stokes Raman Scattering
(CARS) .................................................. 173
Sources of Enhancement of the Raman Signal in Near-
Field Raman Spectroscopy ................................ 173
IR Microscopy beyond the Diffraction Limit: IR Near-Field
Spectroscopy ............................................... 178
Aperture SNOM + IR Spectroscopy ......................... 179
Apertureless SNOM + IR Spectroscopy ..................... 180
Another Source of Enhancement in Near-Field IR
Microscopy: Phonon Excitation ........................... 182
Summary ....................................................... 183
Applications of SPM + Raman Spectroscopy ...................... 185
(Sub-) Monolayers of Dyes .................................. 185
Single-Wall Carbon Nanotubes ............................... 185
Inorganic Materials: Silicon and Semiconductors ............ 187
Biomolecules ............................................... 187
Virus, Bacteria, and Human Cells ........................... 188
Applications of SPM + IR Spectroscopy ......................... 194
Inorganic Materials ........................................ 194
Polymers ................................................... 194
Viruses and Cells .......................................... 195
References .................................................... 199
Chapter 6 Combining the Nanoscopic with the Macroscopic:
SPM and Surface-Sensitive Techniques .......................... 203
Model-Based Surface Techniques ................................ 203
Fundamentals of Surface Plasmon Resonance ..................... 214
Surface Plasmons on Metal Surfaces ......................... 214
Photon Creation/Excitation of SPPs ......................... 217
Experimental SPR ........................................... 219
Fundamentals of Ellipsometry .................................. 221
Basic Equation of Ellipsometry ............................. 221
Single-Layer Model ......................................... 222
Experimental Determination of Ellipsometric Angles ......... 225
Rotating-Element Techniques ................................ 226
Rotating Polarizer/Analyzer ............................. 226
Rotating Compensator .................................... 227
Phase Modulation ........................................ 227
Null Ellipsometry ....................................... 228
Fundamentals of Quartz Crystal Microbalance ................... 229
Electromechanical Analogy of a QCM Sensor: Equivalent
Circuit of a Resonator ..................................... 231
Small-Load Approximation: Connecting Frequency Shifts to
Load Impedance ............................................. 233
Measuring Frequency Shifts and More: Modes of Operation
in QCM ..................................................... 235
Impedance Analysis ...................................... 235
Ring-Down Technique ..................................... 236
Frequency Shifts and Viscoelastic Parameters: Some Case
Examples ................................................... 238
The Special Case of Rigid Films in Air: Sauerbrey
Equation and Film Thickness ............................. 238
Viscoelastic Films and the Importance of Measuring at
Different Overtones ..................................... 239
Main Drawback: The Importance of Qualitative Interpretation 241
Summary ....................................................... 241
The Combination SPM and Model-Based Surface Techniques ........ 241
SPM + SPR ............................................... 241
SPM + Ellipsometry ...................................... 244
SPM + QCM ............................................... 248
References .................................................... 254
Chapter 7 Scanning Probe Microscopy to Measure Surface
Interactions: The Nano Push-Puller ............................ 257
Force Curves: Surface Forces and More ......................... 257
Measuring the Probe-Sample Interaction as a Function of the
Relative Displacement ......................................... 268
Noise and Artifacts ........................................... 272
Quantitative Determination of Forces: Instrument and
Cantilever Calibration ........................................ 273
Voltage to Deflection: Determination of the Sensitivity . 273
Deflection to Force: Determination of Spring Constant ...... 273
The Issue of Getting Absolute Distances ....................... 277
Qualitative Interpretation of Force Curves .................... 280
Chemical Force Microscopy ..................................... 281
The Science of Pulling Single Molecules or Ligand-Receptor
Pairs ......................................................... 282
Statistical Description of Bond Rupture: Two-State Model ... 283
Particularities of Molecular Recognition Spectroscopy ...... 286
Negative Controls ....................................... 286
Inferring Single Ligand-Receptor Interactions from
Adhesion Events ......................................... 287
Particularities of Molecular Unfolding ..................... 288
The Science of Pushing: Contact Nanomechanics ................. 290
A Short Note on Probes for Nanomechanics ................... 290
Contact Region of the Force Curve: Beyond the Point of
Contact .................................................... 291
Mapping Interactions .......................................... 294
Force Curve Maps ........................................... 294
Pulsed Force Mode .......................................... 296
Molecular Recognition Imaging .............................. 297
Summary ....................................................... 298
References .................................................... 300
Chapter 8 Tidying Loose Ends for the Nano Push-Puller:
Microinterferometry and the Film Balance ...................... 303
Microinterferometry ........................................... 393
Fundamentals of Reflection Interference Contrast Microscopy ... 307
Lateral and Vertical Resolution in RICM .................... 311
RICM Setup ................................................. 312
Dual-Wavelength RICM (DW-RICM) ............................. 314
Applications of RICM ....................................... 315
RICM: Summary .............................................. 315
The Combined SPM/RICM Technique ............................... 318
The Film Balance and Air-Fluid Interfaces ..................... 321
Fundamentals of the Film Balance .............................. 325
The Transfer of Monolayers onto Solid Supports ............. 328
The Langmuir-Blodgett Technique ......................... 328
The Langmuir-Schaeffer Technique ........................ 328
The Film Balance: Summary .................................. 329
The Combined AFM + Film Balance: The Monolayer Particle
Interaction Apparatus (MPIA) .................................. 329
References .................................................... 333
Index ......................................................... 335
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