Principles of surface-enhanced Raman spectroscopy

and related plasmonic eects

Eric C. Le Ru and Pablo G. Etchegoin
Preface Notations, units and other conventions 1 A quick overview of surface-enhanced Raman spectroscopy 1.1 What is SERS? Basic principles 1.2 SERS probes and SERS substrates 1.2.1 SERS substrates 1.2.2 SERS probes 1.2.3 Example 1.3 Other important aspects of SERS 1.3.1 SERS enhancements 1.3.2 Sample preparation and metal/probe interaction 1.3.3 Main characteristics of the SERS signals 1.3.4 Related techniques 1.3.5 Related areas 1.4 Applications of SERS 1.4.1 Raman with improved sensitivity 1.4.2 SERS vs uorescence spectroscopy 1.4.3 Applications specic to SERS
PRINCIPLES OF SERS VOLUME ISBN 978-0-444-52779-0

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c Copyright 2009 Elsevier Ltd All rights of reproduction in any form reserved

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1.5 The current status of SERS 1.5.1 Brief history of SERS 1.5.2 Where is SERS now? 1.5.3 Current hot topics 1.6 Overview of the book content 1.6.1 General outline of the book 1.6.2 General spirit of the book 1.6.3 Dierent reading plans 2 Raman spectroscopy and related optical techniques 2.1 A brief introduction 2.1.1 The discovery of the Raman eect 2.1.2 Some applications of Raman spectroscopy 2.1.3 Raman spectroscopy instrumentation 2.2 Optical spectroscopy of molecules 2.2.1 The energy levels of molecules 2.2.2 Spectroscopic units and conversions 2.2.3 Optical absorption 2.2.4 Emission and luminescence 2.2.5 Scattering processes 2.2.6 The concept of cross-section 2.2.7 The Raman cross-sections 2.2.8 Examples of Raman cross-sections 2.2.9 Mechanical analogs 2.3 Absorption and uorescence spectroscopy 2.3.1 Optical absorption and UV/Vis spectroscopy 2.3.2 Fluorescence spectroscopy 2.3.3 Photo-bleaching 2.4 Phenomenological approach to Raman scattering 2.4.1 Dipolar emission in vacuum 2.4.2 The concepts of polarizability and induced dipole 2.4.3 The linear optical polarizability 2.4.4 The Raman polarizability 2.4.5 The local eld correction 2.4.6 Polarizabilities and scattering cross-sections 2.4.7 Final remarks on the phenomenological description 2.5 Vibrations and the Raman tensor 2.5.1 General considerations

PRINCIPLES OF SERS 2.5.2 2.5.3 2.5.4 2.5.5 2.5.6 A primer on vibrational analysis The Raman tensor Link to the Raman polarizability Limitations of the classical approach A brief overview of related Raman scattering processes

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2.6 Quantum (or semi-classical) approach to Raman scattering 2.6.1 Justication of the classical approach 2.6.2 The quantization of vibrations 2.6.3 The full expressions for the Raman cross-section 2.6.4 The anti-Stokes to Stokes ratio 2.7 Advanced aspects of vibrations in molecules 2.7.1 More on vibrational analysis 2.7.2 More on symmetries and Raman selection rules 2.7.3 Modeling of molecular structure and vibrations 2.8 Summary 3 Introduction to plasmons and plasmonics 3.1 Plasmonics and SERS 3.2 The optical properties of noble metals 3.2.1 The Drude model of the optical response 3.2.2 The optical properties of real metals 3.2.3 Non-local optical properties 3.2.4 What makes the metallight interaction so special? 3.3 What are plasmons? 3.3.1 The plasmon confusion 3.3.2 Denition and history 3.3.3 The relation between plasmons and the dielectric function 3.3.4 Electromagnetic modes in innite systems 3.3.5 Electromagnetic modes of a system of material bodies 3.3.6 Classication of electromagnetic modes 3.3.7 Other properties of electromagnetic modes 3.3.8 Summary and discussion 3.4 Surface plasmonpolaritons on planar interfaces 3.4.1 Electromagnetic modes for a planar dielectric/metal interface 3.4.2 Properties of the SPP modes at planar metal/dielectric interfaces 3.4.3 Coupling of PSPP modes with light 3.4.4 PSPP resonances at planar interfaces

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3.4.5 Local eld enhancements and SPPs at planar interfaces 3.4.6 SPP modes on planar interfaces: A brief summary 3.5 Localized surface plasmonpolaritons 3.5.1 Introduction to localized SPPs 3.5.2 LSP on planar structures 3.5.3 LSP modes of a metallic sphere 3.5.4 LSP modes of nano-particles 3.5.5 LSP resonances 3.5.6 Local eld enhancements and LSP 3.5.7 Interaction of SPPs gap SPPs 3.6 Brief survey of plasmonics applications 3.6.1 Applications of surface plasmon resonances 3.6.2 SPP propagation and SPP optics 3.6.3 Local eld enhancements 4 SERS enhancement factors and related topics 4.1 Denition of the SERS enhancement factors 4.1.1 General considerations 4.1.2 The analytical point of view 4.1.3 The SERS substrate enhancement factor Experimental approach 4.1.4 The SERS cross-section and single-molecule EF 4.1.5 The SERS substrate enhancement factor Formal denition 4.1.6 Discussion and merits of the various denitions 4.2 Experimental measurement of SERS enhancement factors 4.2.1 The importance of the non-SERS cross-section 4.2.2 Example of AEF measurements 4.2.3 Link between SSEF denition and experiments 4.3 Overview of the main EM eects in SERS 4.3.1 Analysis of the EM problem of SERS 4.3.2 Local eld enhancement 4.3.3 Radiation enhancement 4.3.4 Other EM eects 4.3.5 The common |E|4 -approximation to SERS enhancements 4.4 Modied spontaneous emission 4.4.1 Introduction 4.4.2 The link between spontaneous emission and dipolar emission 4.4.3 Modication of dipole emission: denitions of enhancement factors

PRINCIPLES OF SERS 4.4.4 Spontaneous emission and self-reaction 4.4.5 The Poynting vector approach 4.4.6 Spontaneous emission and the optical reciprocity theorem 4.5 Formal derivation of SERS EM enhancements 4.5.1 Denitions, notations, and assumptions 4.5.2 The SERS EM enhancement: general case 4.5.3 SERS EM enhancements in the back-scattering conguration 4.6 Surface-enhanced uorescence (SEF) 4.6.1 Similarities and dierences between SEF and SERS 4.6.2 Modied (enhanced) absorption 4.6.3 Modied uorescence quantum yield 4.6.4 Fluorescence quenching and enhancement 4.7 Other EM eects in SERS 4.7.1 Fluorescence quenching in SERS 4.7.2 Photo-bleaching under SERS conditions 4.7.3 Non-radiative eects in SERS 4.8 The chemical enhancement 4.8.1 Introduction 4.8.2 The charge-transfer mechanism 4.8.3 Electromagnetic contribution to the chemical enhancement 4.8.4 The chemical vs electromagnetic enhancement debate 4.9 Summary 5 Calculations of electromagnetic enhancements 5.1 Denition of the problem and approximations 5.1.1 The EM problem 5.1.2 Far eld and local/near eld 5.1.3 Some key EM indicators 5.1.4 The electrostatic approximation (ESA) 5.1.5 Other approximations 5.2 Analytical tools and solutions 5.2.1 Plane surfaces 5.2.2 The perfect sphere 5.2.3 Ellipsoids 5.2.4 Other approaches 5.3 Numerical tools 5.3.1 A brief overview of the EM numerical tools

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5.3.2 A semi-analytical approach: the discrete dipole approximation 5.3.3 Direct numerical solutions 5.3.4 Other approaches 6 EM enhancements and plasmon resonances: examples and discussion 6.1 Quenching and enhancement at planar surfaces 6.1.1 The image dipole approximation for the self-reaction eld 6.1.2 Enhancement and quenching at plane metal surfaces 6.2 A simple example in detail: The metallic sphere 6.2.1 Metallic sphere in the ES approximation 6.2.2 Localized surface plasmon resonances and far-eld properties 6.2.3 Local eld eects 6.2.4 Distance dependence 6.2.5 Non-radiative eects surface-enhanced uorescence 6.3 The eect of shape on the EM enhancements 6.3.1 Shape eects on localized surface plasmon resonances 6.3.2 Shape eects on local elds 6.3.3 Summary of shape eects 6.4 Gap eects junctions between particles 6.4.1 Coupled localized surface plasmon resonances and SERS 6.4.2 EF distribution and hot-spot localization 6.5 Additional eects 6.5.1 Nano-particles on a supporting substrate 6.5.2 Surface roughness 6.6 Factors aecting the EM enhancements: Summary 7 Metallic colloids and other SERS substrates 7.1 Metallic colloids for SERS 7.1.1 Silver vs gold 7.1.2 Citrate-reduced colloids 7.1.3 Other types of colloids 7.1.4 Remarks on colloid fabrication methods 7.1.5 Dry colloids and other 2D planar SERS substrates 7.2 Characterization of SERS substrates 7.2.1 Microscopy

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PRINCIPLES OF SERS 7.2.2 Extinction or UV/Vis spectroscopy of SERS substrates 7.2.3 Other techniques: dynamic light scattering (DLS) for colloidal solutions 7.3 The stability of colloidal solutions 7.3.1 Introduction 7.3.2 The van der Waals interaction between metallic particles 7.3.3 The screened Coulomb potential 7.3.4 The DLVO interaction potential 7.3.5 Colloid aggregation within the DLVO theory 7.4 SERS with metallic colloids 7.4.1 Molecular (analyte) adsorption and SERS activity 7.4.2 Colloid aggregation for SERS 7.4.3 Focus on the chloride activation of SERS signals 7.4.4 SERS from dried colloidal solutions 7.4.5 SERS signal uctuations 8 Recent developments 8.1 Single-molecule SERS 8.1.1 Introduction 8.1.2 Early evidence for single-molecule detection 8.1.3 LangmuirBlodgett monolayers 8.1.4 Bi-analyte techniques 8.1.5 Single-molecule SERS enhancement factors 8.1.6 Single-molecule SERS: Discussion and outlook 8.2 Tip-enhanced Raman spectroscopy (TERS) 8.2.1 Introduction to TERS 8.2.2 TERS with an atomic force microscope (AFM) 8.2.3 TERS with a scanning tunneling microscope (STM) 8.2.4 Theoretical calculations on tips 8.2.5 Discussion and outlook 8.3 New substrates from nano-technology 8.3.1 Chemical synthesis of metallic nano-particles 8.3.2 Self-organization 8.3.3 Nano-lithography 8.3.4 Adaptable/Tunable SERS substrates 8.3.5 Micro-uidics and SERS 8.4 Optical forces 8.4.1 A simple theory of optical forces

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8.4.2 Radiation pressure in colloidal uids 8.4.3 Optical trapping of metallic particles 8.4.4 Optical forces on molecules 8.5 Applications of SERS 8.5.1 Analyte engineering and surface functionalization 8.5.2 Substrate reproducibility and SERS commercialization 8.6 Epilogue

9 Density functional theory (DFT) calculations for Raman spectroscopy 465 A.1 A brief introduction to DFT A.1.1 Computing aspects of DFT A.1.2 Principles of DFT A.1.3 Important parameters A.2 Applications of DFT to Raman A.2.1 Principle A.2.2 Geometry optimization using DFT A.2.3 Limitations of DFT calculations for Raman 465 465 467 469 471 471 472 473

A.3 Practical implementation 474 A.3.1 Brief overview of the input and output les 474 A.3.2 Common units and denitions in Raman calculations from DFT 477 479 A.3.3 Normal mode patterns and Raman tensors A.4 Examples of DFT calculations for SERS applications A.4.1 Validation of absolute Raman cross-sections of reference compounds A.4.2 Raman tensor and vibrational pattern visualizations A.4.3 Depolarization ratio breakdown under SERS conditions B The bond-polarizability model B.1 Principle and implementation B.1.1 Principle B.1.2 Calculation of bond polarizabilities B.1.3 Practical implementation B.2 A simple example in detail B.2.1 Bond-polarizability analysis B.2.2 Raman polarizabilities B.2.3 A brief comment on the symmetry 485 485 485 489 491 491 491 492 495 496 496 497 498

PRINCIPLES OF SERS C A brief overview of Maxwells equations in media C.1 Maxwells equations in vacuum C.1.1 The equations C.1.2 Maxwells equations for harmonic elds in vacuum C.1.3 Plane wave solutions in free-space C.2 Maxwells equations in media C.2.1 Microscopic and macroscopic elds C.2.2 The electromagnetic response of the medium C.2.3 Electric polarization and magnetization C.2.4 Constitutive relations C.2.5 Boundary conditions between two media C.3 Other aspects relevant to SERS and plasmonics C.3.1 The microscopic eld C.3.2 Plane waves in media C.3.3 Electromagnetic problems in SERS C.3.4 Link with the static approach D Lorentz model of the atomic/molecular polarizability D.1 The Lorentz oscillator D.1.1 Principle D.1.2 Multiple transitions (multiple resonances) D.1.3 Example: linear optical polarizability of rhodamine 6G D.2 Link with macroscopic properties D.2.1 Dielectric function in a dilute medium D.2.2 Dielectric function in solids D.2.3 The metallic limit D.3 Summary E Dielectric function of gold and silver E.1 Model dielectric function for silver E.1.1 Analytical expression E.1.2 Comparison to experimental results E.2 Model dielectric function for Au E.2.1 Analytical expression E.2.2 Comparison to experimental results

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E.3 Remarks on the model dielectric functions E.3.1 Limitations of the models E.3.2 Comparison between Ag and Au F Plane waves and planar interfaces F.1 The plane wave electromagnetic elds F.1.1 General expressions F.1.2 Propagating plane waves F.1.3 Evanescent plane waves F.1.4 Inhomogeneous plane waves: hybrid propagating/evanescent waves F.2 Plane waves at a single planar interface F.2.1 Plane wave polarization at an interface F.2.2 General solution for plane waves at a planar interface F.2.3 Physical waves in a semi-innite region F.2.4 The Fresnel coecients F.2.5 Surface modes F.2.6 Incident wave modes F.3 Reection/Refraction at a planar interface F.3.1 Incident, reected, and transmitted waves F.3.2 Snells law F.3.3 TM or p-polarized waves F.3.4 TE or s-polarized waves F.3.5 Special cases F.4 Multi-layer interfaces F.4.1 Principle F.4.2 p-polarized or TM waves F.4.3 s-polarized or TE waves F.4.4 Particular cases of interest F.4.5 Implementation in Matlab F.5 Dipole emission close to a planar interface F.5.1 Total decay rates F.5.2 Radiative decay rates G Ellipsoids in the electrostatic approximation G.1 General case G.1.1 Some denitions G.1.2 Ellipsoidal coordinates

PRINCIPLES OF SERS G.1.3 The electrostatic solution G.1.4 Some important EM indicators for ellipsoids G.1.5 Some aspects of the numerical implementation G.2 Oblate spheroid (pumpkin) G.2.1 Geometrical factors G.2.2 Surface averages G.2.3 Limit of large aspect ratio G.3 Prolate spheroid (rugby ball) G.3.1 Geometrical factors G.3.2 Surface averages G.3.3 Limit of large aspect ratio H Mie theory and its implementation H.1 Introduction H.1.1 Motivation H.1.2 Overview of this appendix H.2 The concepts of Mie theory H.2.1 The electromagnetic equations H.2.2 The vectorial wave equation in spherical coordinates H.2.3 Scattering by a sphere H.2.4 Optical resonances of the sphere H.2.5 Some aspects of the practical implementation of Mie theory H.3 Basic formulas of Mie theory H.3.1 Conventions H.3.2 Spherical coordinates: A brief reminder H.3.3 Denition and properties of the vector spherical harmonics H.3.4 Expressions for the susceptibilities H.3.5 More on optical resonances H.3.6 Absorption, scattering, and extinction for an incident beam H.3.7 Absorption and radiation for a localized source H.3.8 Far-eld radiation prole H.3.9 The local eld at the surface H.4 Plane wave excitation of a sphere: The original Mie theory H.4.1 Expansion of a plane wave in vector spherical harmonics H.4.2 Extinction, scattering, and absorption for plane wave excitation H.4.3 Average local eld at the surface H.4.4 Useful expansions for plane wave excitation

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H.5 Extensions of Mie theory H.5.1 Emitter close to a sphere H.5.2 Coated spheres H.5.3 Multiple spheres and generalized Mie theory (GMT) H.6 Example of implementation of Mie theory with Matlab H.6.1 Common problems H.6.2 Other issues specic to Matlab H.6.3 Some aspects of our implementation References Index