Raman Spectroscopy for Chemical Analysis

CHEMICAL ANALYSIS
A SERIES OF MONOGRAPHS OF ANALYTICAL CHEMISTRY AND ITS APPLICATIONS

Editor

J. D. WINEFORDNER

VOLUME 157

A JOHN WILEY & SONS, INC., PUBLICATION New York / Chichester / Weinheim / Brisbane / Singapore / Toronto

Raman Spectroscopy for Chemical Analysis

RICHARD L. McCREERY
The Ohio State University Columbus, Ohio

A JOHN WILEY & SONS, INC., PUBLICATION New York / Chichester / Weinheim / Brisbane / Singapore / Toronto

This book is printed on acid-free paper. Copyright 2000 by John Wiley & Sons, Inc. All rights reserved. Published simultaneously in Canada. No part of this publication may be reproduced, stored in a retrieval system or transmitted in any form or by any means, electronic, mechanical, photocopying, recording, scanning or otherwise, except as permitted under Sections 107 or 108 of the 1976 United States Copyright Act, without either the prior written permission of the Publisher, or authorization through payment of the appropriate per-copy fee to the Copyright Clearance Center, 222 Rosewood Drive, Danvers, MA 01923, (978) 750-8400, fax (978) 750-4744. Requests to the Publisher for permission should be addressed to the Permissions Department, John Wiley & Sons, Inc., 605 Third Avenue, New York, NY 10158-0012, (212) 850-6011, fax (212) 850-6008, E-mail: PERMREQ@WILEY.COM. For ordering and customer service, call 1-800-CALL-WILEY. Library of Congress Cataloging-in-Publication Data: McCreery, Richard L. Raman spectroscopy for chemical analysis / by Richard L. McCreery. p. cm. (Chemical analysis ; v. 157) A Wiley-interscience publication Includes index ISBN 0-471-25287-5 (alk. paper) 1. Raman spectroscopy. 2. Chemistry, Analytic. I. Title. II. Series. QC454.R36.M33 2000 543.08584 dc21 99-086491 Printed in the United States of America. 10 9 8 7 6 5 4 3 2 1

CONTENTS

PREFACE ACKNOWLEDGMENTS LIST OF SYMBOLS CUMULATIVE LISTING OF VOLUMES IN SERIES CHAPTER 1 1.1. 1.2. 1.3. 1.4. INTRODUCTION AND SCOPE

ix xiii xv xix 1 1 5 10 12 15 15 20 24 30

History Preceding 1986 Technological Advances Comparison to FTIR and NIR Absorption Overview of the Book MAGNITUDE OF RAMAN SCATTERING

CHAPTER 2 2.1. 2.2. 2.3. 2.4.

Theoretical Overview Denition of Raman Cross Section Magnitude of Raman Cross Sections Raman Scattering Intensity COLLECTION AND DETECTION OF RAMAN SCATTERING

CHAPTER 3 3.1. 3.2. 3.3. 3.4.

35 35 37 41 43

Signal Magnitude and Collection Function Instrumental Variables Comprising the Collection Function Spectrometer Response Function Multiplex and Multichannel Spectrometers SIGNAL-TO-NOISE IN RAMAN SPECTROSCOPY

CHAPTER 4

49 49 52

4.1. Denition and Measurement of SNR 4.2. Noise Sources v

vi 4.3. 4.4. 4.5. 4.6.

CONTENTS

Signal-to-Noise Ratio Expressions SNR Figure of Merit SNR and Detection Limits SNR for Multiplex Spectrometers INSTRUMENTATION OVERVIEW AND SPECTROMETER PERFORMANCE

61 65 67 68

CHAPTER 5 5.1. 5.2. 5.3. 5.4. 5.5.

73 74 75 78 79 83

Major Spectrometer Components Laser Wavelength Dispersive vs. Nondispersive Spectrometers Performance Criteria Samples for Spectrometer Evaluation SAMPLING MODES IN RAMAN SPECTROSCOPY

CHAPTER 6 6.1. 6.2. 6.3. 6.4. 6.5. 6.6. 6.7.

95 95 97 99 114 118 120 122 127 127 130 133 134 137 142 149 149 155 179 180 183

Sampling Overview Performance Criteria 180 Backscattering Geometry 90 Sampling Geometry Reducing the Laser Power Density at the Sample Path Length Enhancement Polarization Measurements LASERS FOR RAMAN SPECTROSCOPY

CHAPTER 7 7.1. 7.2. 7.3. 7.4. 7.5. 7.6.

Overview ArC and KrC Ion Lasers HeliumNeon Lasers NeodymiumYAG (Nd:YAG) Diode Lasers Laser Wavelength Filtering DISPERSIVE RAMAN SPECTROMETERS

CHAPTER 8 8.1. 8.2. 8.3. 8.4. 8.5.

Overview Dispersive Spectrometer Congurations Detector Considerations Single-Channel Detectors Multichannel Detectors and CCDs

CONTENTS

vii 203 215

8.6. Recording Methods for Dispersive Spectrometers 8.7. Examples of Dispersive Raman Applications CHAPTER 9 9.1. 9.2. 9.3. 9.4. 9.5. NONDISPERSIVE RAMAN SPECTROMETERS

221 221 225 240 245 246 251 251 251 269 288 289 293 293 295 309 316 333 333 334 337 342 359 364 369 373 373 375

Tunable Bandpass Filters Fourier Transform Raman Spectroscopy Multichannel Fourier Transform Raman Spectroscopy Extensions of FT-Raman for Longer Wavelength Operation FT-Raman Examples

CHAPTER 10 CALIBRATION AND VALIDATION 10.1. 10.2. 10.3. 10.4. 10.5. Overview Frequency and Raman Shift Calibration Instrument Response Function Calibration Absolute Response Calibration Summary of Calibration and Validation Procedures

CHAPTER 11 RAMAN MICROSCOPY AND IMAGING 11.1. 11.2. 11.3. 11.4. Overview of Raman Microscopy Single-Point Raman Microspectroscopy Line Imaging Two-Dimensional Raman Imaging

CHAPTER 12 FIBER-OPTIC RAMAN SAMPLING 12.1. 12.2. 12.3. 12.4. 12.5. 12.6. 12.7. Overview of Fiber-Optic Sampling Fiber-Optic Basics FiberSpectrometer Interface Fiber-Optic Probes Comparisons of Fiber-Optic Sampling Probes Waveguide Sampling for Analytical Raman Spectroscopy Examples of Fiber-Optic Sampling

CHAPTER 13 RAMAN SPECTROSCOPY OF SURFACES 13.1. Overview 13.2. Surface Sensitivity

viii 13.3. 13.4. 13.5. 13.6.

CONTENTS

Sampling Considerations Surface Raman Spectroscopy without Field Enhancement Electromagnetic Field Enhancement Examples of Analytical Applications

379 382 390 409 415

INDEX

PREFACE

This book was inspired by the transition of Raman spectroscopy from a technically demanding research technique to a useful and practical method of chemical analysis. There are many ne texts and thousands of scientic articles on research in Raman spectroscopy, primarily oriented toward understanding the Raman effect itself and using Raman scattering to probe molecular structure and dynamics. These research efforts have reached a high level of sophistication and have yielded valuable chemical and physical insights, but they rarely resulted in practical techniques for chemical analysis until approximately 1986. The impediments to broad applications of Raman spectroscopy to chemical analysis were mainly technological rather than fundamental. The instrumentation required to observe the weak Raman effect was too cumbersome and expensive for routine analysis, and interference from uorescence precluded application to a broad range of industrial samples. As a result, the advantages of Raman spectroscopy over more common infrared absorption techniques were not exploited in analytical problems. Major technological and scientic innovation in the past 10 to 15 years has signicantly broadened the applicability of Raman spectroscopy, particularly in chemical analysis. Fourier transform (FT)Raman, charge-coupled device (CCD) detectors, compact spectrographs, effective laser rejection lters, near-infrared lasers, and small computers have contributed to a revolution in Raman instrumentation and made routine analytical applications possible. An increase in instrumental sensitivity by factors as large as 105 , plus decreases in both interferences and noise resulted from this revolution. The number of vendors of Raman spectrometers increased from 3 to 12 over a 10-year period, and integrated commercial spectrometers led to turnkey operation and robust reliability. This book is intended to introduce a student or practitioner of analytical chemistry to the technical elements and practical benets of the Raman revolution. It is not intended to describe high-end Raman techniques such as nonlinear or time-resolved Raman spectroscopy, nor does it attempt to describe the many theoretical treatments of Raman scattering. The book emphasizes the concepts and technology important to applications of Raman spectroscopy in chemical analysis, with attention to calibration, performance, and sampling modes. While many recent innovations in analytical Raman spectroscopy are ix

PREFACE

technically sophisticated, their objectives are reliability, accuracy, reduction of interferences, and ease of operation rather than ultimate spectral resolution or sensitivity. The emphasis of both the theory and instrumentation discussions in this book is the practical analysis that has resulted from recent technological developments. Techniques such as nonlinear Raman (CARS, hyperRaman, stimulated Raman, etc.), picosecond transient Raman, single-crystal Raman, gas-phase Raman,and so forth are excluded not because they are unimportant, but because they currently have limited use in routine chemical analysis. The audience for this book should include graduate students, practicing chemists, and Raman spectroscopists who seek information on recent instrumentation developments. It is not a comprehensive review but more of a textbook intended as an introduction to modern Raman spectroscopy. In most cases, the techniques discussed are available in commercially available spectrometers, and the book should be useful to chemists who are implementing Raman spectroscopy in industrial or academic laboratories. Although a large number of useful Raman applications involve custom-built instrumentation, the book emphasizes congurations and components used by current vendors of integrated Raman spectrometers. Since commercial spectrometers can be constructed in a variety of congurations, instruments from different manufacturers often differ signicantly in applicability and performance. Specic manufacturers are mentioned in the text to identify a particular approach or optical conguration. Available commercial units differ widely in performance and are often optimized for particular sample types. Mention of a manufacturer in the text does not imply an endorsement but may be useful to the reader in order to appreciate differences in design objectives. There is no best manufacturer or conguration, but certain designs are more applicable to certain situations, depending on the sample and analytical objective. It will become obvious that the sample dictates the choice of spectrometer type, and no single Raman system covers all possible applications. The book is divided into roughly three general areas on theory and instrumentation. Chapters 1 to 4 cover the origin and magnitude of Raman scattering and the major factors determining the signal/noise ratio. Chapters 5 to 10 discuss instrumental components and congurations and methods of calibration. Chapters 11 to 13 address the widely studied specialty areas of Raman microscopy, ber-optic sampling, and Raman spectroscopy of surfaces. In most chapters , many examples of applications to Raman spectroscopy to analytical problems are provided. Notes on Conventions The denitions of several symbols and certain conventions are not used uniformly in the Raman spectroscopy literature, and some choices were

PREFACE

xi

required to retain internal consistency in this book. Raman shifts are plotted from left (low shift) to right (high shift), in opposition to the usual practice for Fourier transform infrared (FTIR) frequencies. Furthermore, the Raman shift axis shows only Stokes-shifted bands unless noted otherwise. The differential Raman cross section is assigned the symbol instead of d /d often used in the literature. As explained in Chapter 2, has specic signicance and is a more convenient symbol for equations. Modern CCD Raman spectrometers count photons rather than measure power, and it is more convenient to dene power and intensity as photons per second and power density as photons per square centimeter per second (Chapter 2). The sampled volume discussed in several texts is explicitly dened herein as the detected area, AD , times the sampling depth, dz. There are several additional and more minor differences in denitions between this book and certain treatments from the literature, and a complete list of symbols is provided to reduce possible confusion.

ACKNOWLEDGMENTS

First and foremost, I thank my wife and children for their support and understanding during the long process of writing this book. Much of the technical information was provided by graduate students in my research group, both past and present. I appreciate their willingness to acquire data not directly related to their research projects. Many technical discussions with practicing spectroscopists were very valuable to the effort, particularly those with Bruce Chase, Chris Frank, Rick Van Duyne, Jack Spencer, Fritz Allen and Jun Zhao. Valuable collaborations with the technical staff at Chromex provided many of the illustrative examples in the book, as well as some innovations in instrument design. Finally, I appreciate the efforts of Margaret Dodd and Anna McCreery with preparation of the manuscript and gures.

xiii

LIST OF SYMBOLS

AD F L R o B P B b S c C D d DS d dz a

polarizability sample area monitored by spectrometer, cm2 scattering coefcient of bers, dB/m scattering and absorption coefcient at laser wavelength, cm scattering and absorption coefcient at laser wavelength, cm polarizability in the absence of vibrations

1 1

differential Raman cross section (d /d ), cm2 molecule 1 sr 1 observed intensity due to background, e rate of background accumulation, e sec 1 frequency independent differential Raman cross section, cm6 sr molecule 1 sample thickness, cm differential Raman cross section for a surface species, cm2 molecule 1 sr 1 speed of light, cm sec 1 collection function for Raman spectrometer, usually cm2 sr e photon 1 cm 1 number density, molecules cm 3 distance between mirrors, cm surface number density, molecule cm 2 increment of observation angle path length increment, cm CCD gain, e /ADU (analog-to-digital converter unit) spectrometer depth of eld, cm spectral resolution, cm 1 molar absorptivity, M 1 , cm 1 blur diameter, cm electric eld, V cm 1 grating efciency into rst order aperture ratio (f number) focal length xv

E EG f/# f1

xvi FS FSNR F0SNR h I0 IR k K

LIST OF SYMBOLS

gure of merit for Raman signal gure of merit based on signal-to-noise ratio, using power density, cm3 sr e (photon) 1 cm3 sr e (photon) 1 CCD gain, e /ADU (analog-to-digital converter unit) mirror velocity in an interferometer, cm sec 1 Plancks constant incident laser intensity, W Raman intensity, W Boltzman constant geometric factor depending on observation geometry, units vary with the situation wavelength, cm specic intensity, photons sec 1 cm 2 sr 1 specic intensity of analyte, photons sec 1 cm 2 sr 1 laser wavelength, nm or cm molar concentration, mol/liter diffraction order frequency of light, Hz number of channels along spectral axis of a multichannel detector refractive index laser frequency number of resolution elements in a given spectrum frequency expressed in wavenumbers vibrational frequency of mode j, expressed in wavenumbers; also Raman shift, in cm 1 frequency of an electronic transition, cm 1 polarization, V cm 1 incident laser power density, photons sec 1 cm 2 incident laser intensity, in photons sec 1 scattered Raman intensity, photons sec 1 rate of dark signal accumulation, e sec 1 average ux of e generated by photons reaching the detector, photons sec 1 quantum efciency of detector, e photon jth normal vibrational mode amplitude of Qj reectivity of focusing mirror
1

L La
0

M m NC n
0

NR
j p

P PD P0 PR d S Q Qj Qj RF

LIST OF SYMBOLS

xvii

S
0 j

Sa S P S P Sa Si S0 i Sbias i Sdark i
B bk d F r S y j

SNR sr RC T T tg tM TS ts Tl TP Tp
v

integrated Raman cross section, cm2 molecule 1 Raman signal, in electrons, e integrated Raman cross section, with intensity stated as photons sec 1 Raman signal, due to analyte band of interest, e mean value of Raman signal, e signal rate, dS/dt, e sec 1 rate of analyte signal accumulation, e sec 1 signal in ith channel (e ) signal in ith channel, in analog-to-digital units (or counts) bias electrons in ith channel dark electrons in ith channel standard deviation of the background (or blank) standard deviation of a blank sample standard deviation of dark signal, sometimes called dark noise icker noise readout noise standard deviation of analyte Raman signal standard deviation of peak height frequency-independent cross section of mode j, cm6 molecule 1 signal noise ratio steradian reectivity of collimating mirror transmission of optics or spectrograph, unitless absolute temperature, K global image acquisition time total spectrum acquisition time, sec. spectrometer transmission single-channel measurement time, or time of observation for a single Raman shift line focus image acquisition time transmission of polarization scrambler point-to-point image acquisition time vibrational quantum number total width of detector radius of beam waist, cm width of pixel or exit slit depth into sample solid angle of collection solid angle observed by the spectrometer at the sample

WD w0 WP z
D

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A SERIES OF MONOGRAPHS ON ANALYTICAL CHEMISTRY AND ITS APPLICATIONS J. D. Winefordner, Series Editor

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