Frontiers of Surface-Enhanced Raman Scattering

List of Contributors xi Preface xv 1. Calculation of Surface-Enhanced Raman Spectra Including Orientational and Stokes Effects Using TDDFT/Mie Theory QM/ED Method 1 George C. Schatz and Nicholas A. Valley 1.1 Introduction: Combined Quantum Mechanics/Electrodynamics Methods 1 1.2 Computational Details 3 1.3 Summary of Model Systems 4 1.4 Azimuthal Averaging 5 1.5 SERS of Pyridine: Models G, A, B, S, and V 6 1.6 Orientation Effects in SERS of Phthalocyanines 11 1.7 Two Particle QM/ED Calculations 13 1.8 Summary 15 Acknowledgment 16 References 16 2. Non-resonant SERS Using the Hottest Hot Spots of Plasmonic Nanoaggregates 19 Katrin Kneipp and Harald Kneipp 2.1 Introduction 19 2.2 Aggregates of Silver and Gold Nanoparticles and Their Hot Spots 21 2.2.1 Evaluation of Plasmonic Nanoaggregates by Vibrational Pumping due to a Non-resonant SERS Process 21 2.2.2 Probing Plasmonic Nanoaggregates by Electron Energy Loss Spectroscopy 24 2.2.3 Probing Local Fields in Hot Spots by SERS and SEHRS 25 2.3 SERS Using Hot Silver Nanoaggregates and Non-resonant NIR Excitation 26 2.3.1 SERS Signal vs. Concentration of the Target Molecule 26 2.3.2 Spectroscopic Potential of Non-resonant SERS Using the Hottest Hot Spots 30 2.4 Summary and Conclusions 31 References 32 3. Effect of Nanoparticle Symmetry on Plasmonic Fields: Implications for Single-Molecule Raman Scattering 37 Lev Chuntonov and Gilad Haran 3.1 Introduction 37 3.2 Methodology 38 3.3 Plasmon Mode Structure of Nanoparticle Clusters 39 3.3.1 Dimers 39 3.3.2 Trimers 40 3.4 Effect of Plasmon Modes on SMSERS 47 3.4.1 Effect of the Spectral Lineshape 47 3.4.2 Effect of Multiple Normal Modes 49 3.5 Conclusions 54 Acknowledgment 54 References 54 4. Experimental Demonstration of Electromagnetic Mechanism of SERS and Quantitative Analysis of SERS Fluctuation Based on the Mechanism 59 Tamitake Itoh 4.1 Experimental Demonstration of the EM Mechanism of SERS 59 4.1.1 Introduction 59 4.1.2 Observations of the EM Mechanism in SERS Spectral Variations 60 4.1.3 Observations of the EM Mechanism in the Refractive Index Dependence of SERS Spectra 62 4.1.4 Quantitative Evaluation of the EM Mechanism of SERS 64 4.1.5 Summary 72 4.2 Quantitative Analysis of SERS Fluctuation Based on the EM Mechanism 72 4.2.1 Introduction 72 4.2.2 Intensity and Spectral Fluctuation in SERS and SEF 73 4.2.3 Framework for Analysis of Fluctuation in SERS and SEF 73 4.2.4 Analysis of Intensity Fluctuation in SERS and SEF 76 4.2.5 Analysis of Spectral Fluctuation in SERS and SEF 78 4.2.6 Summary 82 4.3 Conclusion 82 Acknowledgments 83 References 83 5. Single-Molecule Surface-Enhanced Raman Scattering as a Probe for Adsorption Dynamics on Metal Surfaces 89 Mai Takase, Fumika Nagasawa, Hideki Nabika and Kei Murakoshi 5.1 Introduction 89 5.2 Simultaneous Measurements of Conductance and SERS of a Single-Molecule Junction 90 5.3 SERS Observation Using Heterometallic Nanodimers at the Single-Molecule Level 96 5.4 Conclusion 101 Acknowledgments 101 References 101 6. Analysis of Blinking SERS by a Power Law with an Exponential Function 107 Yasutaka Kitahama and Yukihiro Ozaki 6.1 Introduction 107 6.2 Materials and Methods 110 6.3 Power Law Analysis 110 6.4 Plasmon Resonance Wavelength Dependence 117 6.4.1 Power Law Exponents for the Bright and Dark Events 117 6.4.2 Truncation Time for the Dark Events 123 6.5 Energy Density Dependence 123 6.5.1 Power Law Exponents for the Bright and Dark Events 123 6.5.2 Truncation Time for the Dark Events 125 6.5.3 Comparison with Other Analysis 126 6.6 Temperature Dependence 129 6.6.1 Power Law Exponents for the Bright and Dark Events 129 6.6.2 Truncation Time for the Dark Events 129 6.6.3 Comparison with Other Analysis 130 6.7 Summary 132 Acknowledgments 132 References 133 7. Tip-Enhanced Raman Spectroscopy (TERS) for Nanoscale Imaging and Analysis 139 Taka-aki Yano and Satoshi Kawata 7.1 Crucial Difference between TERS and SERS 139 7.2 TERS-Specific Spectral Change as a Function of Tip-Sample Distance 141 7.3 Mechanical Effect in TERS 143 7.4 Application to Analytical Nano-Imaging 144 7.5 Metallic Probe Tip: Design and Fabrication 149 7.6 Spatial Resolution 154 7.7 Real-Time and 3D Imaging: Perspectives 155 References 156 8. Shell-Isolated Nanoparticle-Enhanced Raman Spectroscopy (SHINERS) 163 Jian-Feng Li and Zhong-Qun Tian 8.1 Introduction 163 8.2 Synthesis of Various Shell-Isolated Nanoparticles (SHINs) 167 8.3 Characterizations of SHINs 169 8.3.1 Correlation of the SHINERS Intensity and Shell Thickness 169 8.3.2 Characterization of the Ultra-Thin Uniform Silica Shell 171 8.3.3 Influence of the SHINs on the Surface 172 8.4 Applications of SHINERS 173 8.4.1 Single-Crystal Electrode Surface 173 8.4.2 Non-Metallic Material Surfaces 175 8.4.3 Single Particle SHINERS 178 8.5 Different Strategies of SHINERS Compared to Previous SERS Works Using Core-Shell or Overlayer Structures 178 8.6 Advantages of Isolated Mode over Contact Mode 180 8.7 Concluding Discussion 184 8.8 Outlook 185 Acknowledgments 186 References 186 9. Applying Super-Resolution Imaging Techniques to Problems in Single-Molecule SERS 193 Eric J. Titus and Katherine A. Willets 9.1 Introduction 193 9.1.1 Single-Molecule Surface-Enhanced Raman Scattering (SM-SERS) 193 9.1.2 Super-Resolution Imaging 194 9.2 Experimental Considerations for Super-Resolution SM-SERS 195 9.2.1 Sample Preparation 195 9.2.2 Instrument Set-up 196 9.2.3 Camera Pixels and Theoretical Uncertainties 197 9.2.4 Correlated Imaging and Spectroscopy in Super-Resolution SM-SERS 198 9.2.5 Correlated Optical and Structural Data 199 9.3 Super-Resolution SM-SERS Analysis 200 9.3.1 Mechanical Drift Correction 201 9.3.2 Analysis of Background Nanoparticle Luminescence 202 9.3.3 Calculating the SM-SERS Centroid Position 202 9.4 Super-Resolution SM-SERS Examples 204 9.4.1 Mapping SM-SERS Hot Spots 204 9.4.2 The Role of Plasmon-Enhanced Electromagnetic Fields: Structure Correlation Studies 206 9.4.3 The Role of the Molecule: Isotope-Edited Studies 210 9.5 Conclusions 214 References 214 10. Lithographically-Fabricated SERS Substrates: Double Resonances, Nanogaps, and Beamed Emission 219 Kenneth B. Crozier, Wenqi Zhu, Yizhuo Chu, Dongxing Wang and Mohamad Banaee 10.1 Introduction 219 10.2 Double Resonance SERS Substrates 220 10.3 Lithographically-Fabricated Nanogap Dimers 226 10.4 Beamed Raman Scattering 229 10.5 Conclusions 238 References 239 11. Plasmon-Enhanced Scattering and Fluorescence Used for Ultrasensitive Detection in Langmuir-Blodgett Monolayers 243 Diogo Volpati, Aisha Alsaleh, Carlos J. L. Constantino and Ricardo F. Aroca 11.1 Introduction 243 11.2 Surface-Enhanced Resonance Raman Scattering of Tagged Phospholipids 245 11.2.1 Experimental Details 245 11.2.2 Langmuir and LB films 246 11.2.3 Electronic Absorption 247 11.2.4 Characteristic Vibrational Modes of the Tagged Phospholipid 248 11.2.5 Single Molecule Detection 250 11.3 Shell-Isolated Nanoparticle Enhanced Fluorescence (SHINEF) 251 11.3.1 Tuning the Enhancement Factor in SHINEF 251 11.3.2 SHINEF of Fluorescein-DHPE 253 11.4 Conclusions 254 Acknowledgments 255 References 255 12. SERS Analysis of Bacteria, Human Blood, and Cancer Cells: a Metabolomic and Diagnostic Tool 257 W. Ranjith Premasiri, Paul Lemler, Ying Chen, Yoseph Gebregziabher and Lawrence D. Ziegler 12.1 Introduction 257 12.2 SERS of Bacterial Cells: Methodology and Diagnostics 258 12.3 Characteristics of SERS Spectra of Bacteria 261 12.4 PCA Barcode Analysis 263 12.5 Biological Origins of Bacterial SERS Signatures 265 12.6 SERS Bacterial Identification in Human Body Fluids: Bacteremia and UTI Diagnostics 266 12.7 Red Blood Cells and Hemoglobin: Blood Aging and Disease Detection 267 12.8 SERS of Whole Blood 269 12.9 SERS of RBCs 271 12.10 Malaria Detection 273 12.11 Cancer Cell Detection: Metabolic Profiling by SERS 273 12.12 Conclusions 276 Acknowledgment 277 References 277 13. SERS in Cells: from Concepts to Practical Applications 285 Janina Kneipp and Daniela Drescher 13.1 Introduction 285 13.2 SERS Labels and SERS Nanoprobes: Different Approaches to Obtain Different Information 286 13.2.1 Highlighting Cellular Substructures with SERS Labels 286 13.2.2 Probing Intrinsic Cellular Biochemistry with SERS Nanoprobes 288 13.3 Consequences of Endocytotic Uptake and Processing for Intrinsic SERS Probing in Cells 289 13.4 Quantification of Metal Nanoparticles in Cells 292 13.5 Toxicity Considerations 295 13.6 Applications 298 13.6.1 pH Nanosensors for Studies in Live Cells 298 13.6.2 Following Cell Division with SERS 299 Acknowledgment 301 References 301 Index 309